CN1061445A - Use alkyl aluminum hydride to form with the method for aluminium as the metal deposition film of principal constituent - Google Patents
Use alkyl aluminum hydride to form with the method for aluminium as the metal deposition film of principal constituent Download PDFInfo
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- CN1061445A CN1061445A CN91101919A CN91101919A CN1061445A CN 1061445 A CN1061445 A CN 1061445A CN 91101919 A CN91101919 A CN 91101919A CN 91101919 A CN91101919 A CN 91101919A CN 1061445 A CN1061445 A CN 1061445A
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- 238000000034 method Methods 0.000 title claims abstract description 115
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 64
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000004411 aluminium Substances 0.000 title claims abstract description 42
- 125000005234 alkyl aluminium group Chemical group 0.000 title claims abstract description 27
- 239000000470 constituent Substances 0.000 title claims abstract description 4
- 238000001465 metallisation Methods 0.000 title description 7
- 239000000758 substrate Substances 0.000 claims abstract description 325
- 239000007789 gas Substances 0.000 claims abstract description 131
- 238000010438 heat treatment Methods 0.000 claims abstract description 79
- 239000012528 membrane Substances 0.000 claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000008021 deposition Effects 0.000 claims description 192
- 230000015572 biosynthetic process Effects 0.000 claims description 73
- 229910052710 silicon Inorganic materials 0.000 claims description 66
- 239000004065 semiconductor Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000012808 vapor phase Substances 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims 3
- 239000010408 film Substances 0.000 description 402
- 238000000151 deposition Methods 0.000 description 266
- 238000005229 chemical vapour deposition Methods 0.000 description 80
- 238000004062 sedimentation Methods 0.000 description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 62
- 239000010703 silicon Substances 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 58
- 239000000463 material Substances 0.000 description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 48
- 239000013078 crystal Substances 0.000 description 47
- 229910052751 metal Inorganic materials 0.000 description 45
- 239000002184 metal Substances 0.000 description 45
- 238000004544 sputter deposition Methods 0.000 description 41
- 238000005530 etching Methods 0.000 description 40
- 239000010949 copper Substances 0.000 description 37
- 229910004298 SiO 2 Inorganic materials 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 31
- 229910052786 argon Inorganic materials 0.000 description 26
- 229910018594 Si-Cu Inorganic materials 0.000 description 25
- 229910008465 Si—Cu Inorganic materials 0.000 description 25
- 229910018182 Al—Cu Inorganic materials 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 23
- 238000012546 transfer Methods 0.000 description 22
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 18
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- -1 aluminium-silicon-copper Chemical compound 0.000 description 13
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 229910008332 Si-Ti Inorganic materials 0.000 description 10
- 229910006749 Si—Ti Inorganic materials 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000002310 reflectometry Methods 0.000 description 10
- 229910052715 tantalum Inorganic materials 0.000 description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 10
- 235000012431 wafers Nutrition 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000002075 main ingredient Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 8
- 229910000091 aluminium hydride Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 7
- 229910021419 crystalline silicon Inorganic materials 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910021332 silicide Inorganic materials 0.000 description 6
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000005380 borophosphosilicate glass Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000001459 lithography Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 2
- JUZTWRXHHZRLED-UHFFFAOYSA-N [Si].[Cu].[Cu].[Cu].[Cu].[Cu] Chemical compound [Si].[Cu].[Cu].[Cu].[Cu].[Cu] JUZTWRXHHZRLED-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910021360 copper silicide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000000427 thin-film deposition Methods 0.000 description 2
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 2
- 229910021342 tungsten silicide Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical class CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001485 argon Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910021341 titanium silicide Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/32051—Deposition of metallic or metal-silicide layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
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- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Chemical Vapour Deposition (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A kind of method that forms metallic membrane may further comprise the steps: settle in the space for forming the used substrate of film; In this space, introduce alkyl aluminum hydride gas and hydrogen; And this substrate of direct heating and on this substrate, form and contain the metallic membrane that principal constituent is an aluminium.
Description
The present invention relates to a kind of method that forms the metal deposition film, particularly relate to and form the method be suitable for preferentially as the metal deposition film of the circuit of things such as semiconductor device.
For electron device or electrode in the unicircuit or the lead that semi-conductor of the prior art adopted, mainly adopt aluminium (Al) or siliceous aluminium (Al-Si) etc.This is because the low price of aluminium, high electric conductivity is arranged, and also form fine and close oxide film in its surface, make aluminium have lot of advantages by this oxide film, for example its inside can obtain chemical protection and make it stable, and the adhesion property of itself and Si is good etc.
And improve such as the degree of integration of the unicircuit of LSI etc. in recent years, and particularly require to form meticulous circuit and multilayer line.So more austere requirement because that circuit has been proposed not run into as yet up to now.For example, in dynamical RAM such as 4 megabits or 1,000 6 megabits etc., its inner aspect ratio (hole depth: be 1.0 or bigger the aperture) that must deposit as the hole (via hole) of metals such as Al.The diameter in this hole itself is 1 micron or littler, thus also demand can be in having the hole of larger ratio of height to diameter more the technology of depositing Al.
In addition, for making related semiconductor device in commercial achieving success, this technology must be able to be produced by batch with low cost.
In the art, sputtering method, vapor phase process-as all being known as forming as the CVD method of aluminium film etc. by adopting trimethyl aluminium etc.Particularly hot CVD (chemical vapour deposition) method various researchs have been done.For example, used such method: the organoaluminum that is dispersed in this method in the carrier gas is taken on heated surface, this gas molecule thermolysis and form a skim on this surface then.And for example described in " Journal of Electrochemical Society Vol.131, P.2175(1984) ", by adopting triisobutyl aluminium (i-C
4H
9)
3Al(TIBA), depress and carry out film forming at 260 ° film-forming temperatures, 0.5 reaction tubes that holds in the palm, the result forms the film of 3.4 μ Ω .cm.
Owing to reasons such as substep coating and electromigration, the surface smoothness of Al is very poor, and can not get high-quality film yet according to the method.In addition, the Al in the hole is not fine and close yet.
The open No.63-33569 of Japanese Patent has disclosed near a kind of organic Al of heating substrate and film forming method.According to this method, can Al optionally be deposited on the metal or semiconductor surface of the substrate that has been eliminated natural oxide film the CVD method.The document has further been narrated after these holes are coated with Al and with sputtering method Al has been deposited on this oxide film.
Yet, also be according to this method because not enough as the surface smoothness of the Al in the hole of main prerequisite, the result make the Al film that forms by the CVD method the intermembranous interface poor electric contact of Al that forms by sputtering method and cause the resistance rising.
Improvement example as this method is: by the double wall CVD method of " 2nd Symposium of Electro-chemical Society; Branch of Japan(July 7th; 1989) P.75 " narration, this method can optionally only grow Al by adopting TIBA gas on metal or semi-conductor.Yet difficulty is the temperature difference that is difficult between accurate pilot-gas temperature and substrate surface temperature, and must heat gas cylinder (bomb) and circuit, and this has just caused the complicated shortcoming of apparatus structure.
The more important thing is: if everything can not get control, the device that then forms the metal deposition film can be complicated, and have to adopt the processing of wafers mode, and in this mode, only can on wafer, deposit with a kind of deposition procedures, in addition, with 500 dusts/minute sedimentation velocity have to the bad film of quality, and can not constitute with the highest such sedimentation velocity and to produce required throughput by batch.In addition, unless make certain thickness, even the film that obtains according to this method can not form even successive film yet so.Thereby confirmed that this method is unsafty and is to be unsuitable for mass-productedly that this is because the planeness of film is not good, the selectivity during the Al selective growth can not keep sufficiently long time etc. former thereby make that its circulation ratio is very poor.
Moreover, when adopting a kind of device that forms metallic membrane, for being carried out to membrane operations or maintenance, being used for gas film forming or that be used for chamber cleaning and introducing this chamber various, to carry out required processing.When carrying out as symphysis is continuous, handle though finished this class, even in the CVD method that only has a spot of things such as carbon that derive from the organoaluminum raw material, still worrying has other impurity outside the de-carbon to be wrapped up in the medium problem in this interface of being with.This problem may become the unexpected reason that descends of the semiconducter device productive rate that makes batch process.
As mentioned above, CVD method according to prior art, all can not be satisfactory for the improvement of producing very necessary sedimentation velocity of semiconductor device and throughput aspect with low cost by batch, but also exist the selective growth of high-quality Al can be reached, but owing to reasons such as fine and close Al formation in planeness, purity and layering topped (step coverage) contact hole, problem is still existed, so circulation ratio still is very poor.Like this, for the more improvement of high integration, still have and fill a part improvable leeway.
The objective of the invention is to improve above-mentioned technical problem and a kind of method that forms metallic membrane is provided,, also can obtain metallic membrane with good circulation ratio, high sedimentation velocity and high productivity even need not complicated and expensive deposition membrane formation device with this method.
Another object of the present invention provides a kind of method that can form metallic membrane in the hole of larger ratio of height to diameter.
It is the method for very superior metallic membrane that a further object of the present invention provides a kind of formation as the electrode of semiconducter device and line material, why so be since by in the hole by metal with superior optionally film depositing high-quality, and then on all surfaces that comprises the barrier film surface, deposit this metal by non-selective one-tenth embrane method, at first be deposited in this hole thereby improved, superior metal of electroconductibility and planeness and contacting between the sedimentary metallic membrane after this, so just have low resistivity, and also be firm for electromigration.
Even a further object of the present invention provides the film of also not bringing impurity after our film deposition system is reused for a long time substantially into.
For reaching these purposes, the present invention includes the following step: substrate is placed be used for film forming space; Alkyl aluminum hydride gas and hydrogen are introduced in this space; This substrate of direct heating is the metallic membrane of main composition to form in its surface with aluminium then.
Certainly, if desired, the gas of the dvielement by will containing Si when film forming introduces together that just can to form such as Al-Si etc. be the metallic membrane of main composition with Al.
In the present invention, by this substrate of direct heating when the selective deposition aluminium, the sedimentation velocity that just can exceed people's expectation forms the metallic membrane with superior membrane property.
According to the present invention, because employing as the snead process of lamp and so on, then supplies hydrogen atom on the surface of electron donor(ED) by impelling, and keeps reliable selectivity that sedimentation velocity is improved simultaneously.
The improvement of sedimentation velocity has not only improved throughput, even and be brought into easily at impurity under the mal-condition of metallic membrane, also can produce the effect that prevents that impurity from bringing into.Therefore the quality and the throughput of film all can be improved simultaneously, can demonstrate compelling effect in the field of preparation semiconducter device whereby.
Wrap up in that the problem of band impurity is also available to be had so-called multicellular metal membrane formation device and improve, in this device, the Al film is formed step be divided into selective deposition and two steps of non-selective deposition, and each reaction chamber of two steps is connected with each other together, so that carry out two above-mentioned steps continuously.
For achieving the above object, the present invention has the following step: substrate is placed first filming chamber; Alkyl aluminum hydride gas and hydrogen are introduced in this first filming chamber; Heated substrate is so that form the aluminium film in its surface; Under the condition of isolated outside air, this substrate is moved in second filming chamber of next-door neighbour first filming chamber setting then, form metallic membrane on this surface so that can completely cut off outside air continuously and press vapor phase process.
The Al that optionally is deposited among the contact hole becomes a kind of high-quality monocrystal material, thereby forms the fabulous dense film of surface finish.And then, by this substrate being continued to pass through filming chamber and don't being exposed in the outside air, then carry out selectivity/non-selective deposition serially.When carrying out selective deposition, based on DMAH and H at low temperatures
2The surface reaction of gas optionally is deposited in the contact hole Al.Because this Al has fabulous optionally high quality Al film,,, can constitute multilayer line whereby on sealing coat so layer of metal film must be non-selectively formed again for it being used line material as semiconducter device.Like this, the Al film that is deposited in the contact hole is exactly the fabulous monocrystalline of surface finish.Because the barrier film surface comprises the surface of this monocrystalline, even so in the time may forming metallic membrane such as Al with sputtering method or CVD method, also can remain on Al film good contact intermembranous of such formation, can obtain the Al film littler whereby than resistance with the Al of selective deposition in contact hole.
For achieving the above object, the present invention also comprises the following steps: substrate is placed first filming chamber; Alkyl aluminum hydride gas, the gas that contains element silicon and hydrogen are introduced first filming chamber; Heat this substrate to deposit layer of aluminum-silicon fiml in its surface; Under the condition of isolated outside air, move this substrate and,, and on this substrate, form layer of metal film with vapor phase process so that can completely cut off extraneous air continuously with it second filming chamber that places next-door neighbour first filming chamber to be provided with.
This Al-Si that is selectively deposited in the contact hole becomes a kind of high-quality monocrystal material, thereby forms the film of the fabulous densification of surface finish.And then, owing to this substrate being moved continuously and don't being exposed in the outside air, just can carry out selectivity/non-selective deposition continuously, when carrying out selective deposition, based on the DMAH under the low temperature, silicon-containing gas and H in this filming chamber
2The surface reaction of gas optionally is deposited on Al-Si in the contact hole.Because this Al-Si is the fabulous high quality Al-Si film of selectivity, is with it line material as semiconducter device, then must further layer of metal film be non-selectively formed on this sealing coat, realizes multilayer line whereby.At this, the Al-Si film of having found to be deposited in the contact hole is the fabulous monocrystalline of surface finish.As for the barrier film surface that comprises this monocrystalline Al-Si surface, even pressing sputtering method or CVD method when forming metallic membrane as Al and so on, also can obtain the Al film littler whereby at the metallic membrane and good being connected of the intermembranous maintenance of Al that optionally is deposited in the contact hole that form like this than resistance.
Fig. 1 shows an embodiment synoptic diagram that is used to implement preferred metal membrane formation device of the present invention;
Fig. 2 is the synoptic diagram that is used for diagram metal of the present invention formation method;
Fig. 3 shows an embodiment being suitable for the continuous formation preferred metal film device of comparing with the present invention;
Fig. 4-Fig. 6 has showed an embodiment of the device that is used to implement continuous formation preferred metal film of the present invention;
Fig. 4 has showed the synoptic diagram of series arrangement step;
Fig. 5 is a structural representation;
Fig. 6 is the structural representation similar to Fig. 5, yet has added the motion of pressing the arrow indication;
Fig. 7 shows the another kind of embodiment synoptic diagram that is used to implement the device of continuous formation preferred metal film of the present invention;
Fig. 8 is a synoptic diagram of showing the mode of selective deposition Al;
Fig. 9 shows to be used for preferable CVD schematic representation of apparatus of the present invention.
Before being described in detail the present invention, at first narrate below the better film build method (Al-CVD method) that is applicable to the metal film that (comprises pure Al) take Al as main composition of the present invention.
The method be a kind of be suitable for metal charge embedding ratio such as precision with dark, ratio of height to diameter be 1 or the method for larger hole (contact hole, pass through the hole), and be a kind of selective splendid deposition process.
The metal film that forms in this way such as forming monocrystalline Al, be very superior in crystallinity, and it only contains a small amount of things such as carbon.
This method is a kind of by adopting alkyl aluminum hydride gas and hydrogen, reacts and the method for formation deposited film through the substrate surface at electron donor. Especially pass through the methylic alkyl aluminum hydride of employing such as monomethyl alanate (MMAH) or dimethyl alanate (DMAH) as unstrpped gas, adopt H2Gas is as reacting gas, and under the mixture conditions of these gases heated substrate surface and deposit high-quality Al film.
Impose the CVD method by surface part and non-electronic this substrate of body part coexistence of giving at electron donor, then with good selective only at the substrate surface part formation monocrystal Al of electron donor.
Electron donor material refers to a kind of like this material: because the existence of free electron or have a mind to form free electron in the substrate, it has by providing or obtain electronics and the surface of the molecular raw material gas chemically reactive that is attached to this substrate surface. For example, metal and semiconductor are exactly like this usually. Have the material that thin metallized metal oxidation film exists at this metal or semiconductor surface, bearing by between substrate and appended raw molecule, providing and obtain the chemical reaction that carry out the electron institute, thereby they are also included within the electron donor material of the present invention.
The instantiation of electron donor material comprises: the group Ⅲ-Ⅴ compound semiconductor that contains combined binary system, quaternary system or polynary system such as the element Ga of III family, In, Al etc. and group Ⅴ element P, As, N etc.; Such as monocrystalline silicon, the semi-conducting materials such as the P-type of amorphism silicon etc., I-type, N-type; Following metal, alloy, silicide etc. are such as tungsten, molybdenum, tantalum, copper, titanium, aluminium, titanium-aluminium, titanium nitride, aluminium-silicon-copper, aluminium palladium, tungsten silicide, titanium silicide, silicated aluminum, copper silicide, tantalum silicide etc.
On the other hand, as the Al that forms non-selective deposition or the material on Al-Si surface, the example that is non-electronic donor material has glass, oxidation film, hot nitride films such as the silica that forms through methods such as thermal oxide, CVD, BSG, PSG, BPSG, and with formed silicon nitride films of method such as plasma CVD method, decompression CVD method, ECR-CVD.
According to the Al-CVD method, also can select to deposit and contain modifying element and the metal film take Al as main composition, and the quality of this film also presents extremely good characteristic.
For example, except alkyl aluminum hydride gas and hydrogen, can also be at an easy rate with such as SiH4、Si
2H
6、Si
3H
8、Si（CH
3）
4、SiCl
4、SiH
2Cl
2、SiHCl
3Deng the gas that contains element silicon;
Such as TiCl4、TiBr
4、Ti（CH
3）
4Deng the gas that contains the Ti element;
Bis-acetylacetonate hydrochlorate Cu(C such as copper5H
7O
2）
2, copper two dipivaloylmethane compounds (Copper bisdipivaloyl methanite) Cu(C11H
19O
2）
2, copper two hexafluoroacetylacetone hydrochlorate Cu(C5HF
6O
2）
2Mix and import to form a kind of mixed atmosphere Deng the gas that contains copper, optionally deposit whereby conductive materials such as Al-Si, Al-Ti, Al-Cu, Al-Si-Ti, Al-Si-Cu and form electrode.
Because above-mentioned Al-CVD method also is a kind of selective splendid film build method, and can make film that this is deposited obtain good surface characteristic, therefore by in lower one deposition step, adopt non-selective be deposited as embrane method again on the Al of above-mentioned selective deposition film with barrier film SiO2Deng upper Al or the metal film take Al as Main Ingredients and Appearance of forming, has the suitable metal film of highly versatile in the time of so just can obtaining as the semiconductor devices circuit. This method will be narrated hereinafter as better embodiment of the present invention.
Hereinafter will narrate specially this metal film, that is to say that it is Al, Al-Si, Al-Ti, the Al-Cu of Al, Al-Si, Al-Ti, Al-Cu, Al-Si-Ti, Al-Si-Cu and the non-selective deposition of selective deposition, the combination of Al-Si-Ti, Al-Si-Cu. Except above-mentioned Al-CVD method, sputtering method etc., also have various CVD methods as the one-tenth embrane method of non-selective deposition.
As desiring by non-selective sedimentary this metallic membrane, can adopt to contain W, Mo etc. is the metal of main composition.
Describe the present invention by the specific embodiment of reference now, but the present invention is not limited to these embodiments described below, but is comprising the embodiment of various remodeling, so just have the various structures that can reach the object of the invention.
In one embodiment of the invention, when adopting at least two kinds of alkyl aluminum hydride gases and hydrogen on substrate, to form the Al film, by just forming the metal deposition film with this substrate surfaces of thing direct heating such as lamps.
This can formation by the present invention is that the metallic membrane of main composition can comprise the combination as pure Al and non-selective sedimentary pure Al, pure Al and Al-Sr, pure Al and Al-Cu, Al and Al-Si-Cu, Al and Al-Ti, Al and the Al-Si-Ti etc. of selective deposition with Al.
Especially make unstripped gas with monomethyl alanate (MMAH) and/or dimethyl alanate (DMAH), use H
2Make reactant gases, and, just can high sedimentation velocity form high-quality Al film by this substrate surface of direct heating (lamp heating) under the mixture of these gases.
Like this, be during the Al film forms, to keep 260 ℃-440 ℃ preferable substrate surface temperature, be not heated by resistive and with this substrate surface of lamp direct heating, whereby just can the 3000-5000 dust/minute high sedimentation velocity obtain high-quality film.
More than at being that the embodiment of pure Al of the metallic membrane of main composition is described as unstripped gas deposition with Al by only adopting organoaluminum gas.In the present invention also may be on substrate selective deposition contain the aluminium of modifying element, in the time of as aluminium-silicon (Al-Si), form metallic membrane with high sedimentation velocity with excellent film characteristic by this substrate of direct heating.
In this embodiment of the present invention, when adopting alkyl aluminum hydride gas, the gas that contains element silicon and hydrogen on substrate, to form the Al film, just can form the metal deposition film by adopting these substrate surfaces of thing direct heating such as lamp.
Thisly can comprise being main composition and containing combination of selective deposition by the metallic membrane that the present invention forms as metal and non-selective sedimentary Al-Si, Al-Si and Al-Cu, Al-Si and Al-Si-Cu, Al-Si and Al-Ti, Al-Si and the Al-Si-Ti etc. of modifying elements such as Al-Si with aluminium.
Especially, adopt above-mentioned monomethyl alanate (MMAH) and/or dimethyl alanate (DMAH) and contain gas as silicon and so on modifying element, use H as unstripped gas
2Gas is made reactant gases and obtained high-quality by the sedimentation velocity that this substrate surface of direct heating just can be high under the mixture of these gases is the metallic membrane of main composition with Al.
Like this, also be during the Al-Si film forms, for keeping 260 ℃-440 ℃ preferable substrate surface temperature, be not heated by resistive substrate, but with lamp direct heating substrate surface, but with regard to the 3000-5000 dust/minute high sedimentation velocity obtain high-quality film.The narration of metal foil membrane formation device (1)
The embodiment of the direct heating system that adopts the lamp heating at first, is described with the used a kind of preferable metal membrane formation device of the present invention.
Fig. 1 has showed a kind of used preferable metal membrane formation device of the present invention that is.
Metallic film forms on substrate 109, and substrate 109 is fixed on the base sheet rack 110 that is positioned at reaction chamber 101, and reaction chamber 101 is transparent insulations, is made by founding quartz etc.The gas system of infeeding comprises mixing tank 104 and bubbler 105, also comprise the hydrogen ingress pipe 111 that is used for bubbling, it is first gas duct that communicates with mixing tank 104 by the bubbler 105 that holds DMAH, hydrogen ingress pipe 111A, it is second gas duct that communicates with mixing tank 104, and is used for DMAH gas and hydrogen are introduced the gas inlet tube 112 that reaction chamber 101 is introduced in hole 106 by gas.In addition, when introducing other gas 115 also as gas inlet tube.Pumped vacuum systems 107 has a vacuum pump, and comprise one with vacuumize the vacuum-pumping tube 113 that hole 108 communicates.
Use this film forming device, can make the substrate surface temperature-stable in desired temperature through heating 5 seconds or less time, the structure of this device can also obtain high yield, so that reach the wafer of per hour handling 5 inches of 15-30 sheets.
Can be used as and carry out direct-fired device and comprise such as light sources such as halogen lamp, xenon lamps.
More precisely, it is not as a kind of device of resistive heating, but a kind of handle comes the energy of self-heating apparatus to be directly delivered to the device to heat on the substrate surface.When being heated by resistive, substrate surface is to heat to the heat passage of front surface by the rear surface from the stand of placing substrate.Should be pointed out that this is different with optics CVD method by utilizing the UV ray to carry out optical excitation.
The narration of metal formation method (1)
Then, with reference to Fig. 2 in detail the preferred metallic film formation method of using among the present invention is described in detail.
Sedimentary substrate is treated in preparation, forms insulating film 2 having the electron donor(ED) surface and contain on the substrate 1 of semi-conductor or conductor material, and this insulating film has the aperture (VH of various diameters
1, VH
2).Here, the surface of insulating film 2 is non-electron donor(ED) surface (Fig. 2 A).
Then, the CVD method according to using alkyl aluminium hydride and hydrogen has formed the metallic film of Al as main ingredient.For this purpose, substrate is placed in the reaction chamber 101, in reaction chamber, after the decompression, the gaseous mixture of alkyl aluminium hydride and hydrogen is introduced reaction chamber.Turn on the light and make the substrate surface temperature remain on 260 ℃ to 440 ℃, be more preferred from 270 ℃ to 440 ℃, aluminium is optionally deposited in each hole.On the basis through testing predetermined sedimentation velocity, aluminium is deposited to the height almost same with the insulating film surface (Fig. 2 B).
Then, for being formed for the circuit of semiconductor device, with al deposition to whole surface.For this purpose, the reaction chamber of substrate by Fig. 1 taken out, put into the reaction chamber of another deposition of thin membrane formation device, and according to known sputtering method of affiliated technical field or CVD method deposition of aluminum (Fig. 2 C).
According to present understanding, the mechanism of al deposition is as described below.
Promptly have attached to the substrate of electron donor(ED) at hydrogen atom under the on-chip situation of electronics (Fig. 8 A), when the DMAH that has a methyl group arrives the face of substrate, the electronics of substrate will cut off the key (Fig. 8 B and 8C) between aluminium and the methyl.
The reaction of this moment is as follows:
In addition, for the hydrogen atom of staying on the sedimentary Al with unbound electron, reaction will be proceeded (Fig. 8 D) similarly.At this, when lacking hydrogen atom, the hydrogen molecule of reactant gases will decompose and hydrogen atom will be provided.And on the surface of non-electron donor(ED),, just do not have the deposition of Al because there is not the above-mentioned reaction of electronics not carry out yet.
Thereby, for obtaining high sedimentation velocity, importantly start decomposition-absorption reaction, and make hydrogen molecule resolve into hydrogen atom and they are adsorbed on the electron donor(ED) surface.Direct heating promotes selective deposition with regard to playing this effect.
To by with direct heating such as lamps and use DMAH and H as alkyl aluminium hydride
2The Al film that obtains, and be heated by resistive by device shown in Figure 3 substrate is heated to 260 ℃ and the Al film that obtains compares.
Discovery is heated by resistive not carbon containing and have good resistivity of Al film that method obtains, but depositing of thin film speed maximum be 800 dusts/minute.This high speed of must not saying so.So, attempt to improve sedimentation velocity by improving substrate temperature, but produced surface shape with deterioration, the resistivity that reduced or the sample of non-selectivity.Thereby the inventor finds, only produced the problem of relevant reproducibility with the method for raising substrate temperature.
The present invention also attempts to improve sedimentation velocity meticulously by the method that increases the DMAH gas flow.Yet also observe the surface shape that sample has deterioration in this case, find still to exist according to the method the problem of relevant reproducibility thus.
, sedimentary pure Al presents single crystal structure in the hole according to the method described above, and it has good performance, for example:
(1) reduced the occurrence probability of hillock;
(2) reduced the occurrence probability of the local turmoil of alloy lattice (spike).
Aforesaid method is a kind of fabulous deposition method with regard to selectivity and precision work, similar with the situation of above-mentioned pure Al, it is in order to compare with snead processes such as using lamp, by using non-selective deposition method as the deposition step that continues, the present invention is also by using as the DMAH of alkyl aluminium hydride, the gas that contains element silicon and hydrogen, and the method that is heated by resistive is heated to 260 ℃ to form the Al-Si film with substrate.
The Al-Si film of Huo Deing carbon containing and have good resistivity not according to the method, but depositing of thin film speed maximum be 800 dusts/minute, this never talkative one-tenth is high speed.So attempt to improve sedimentation velocity, but produced surface shape, low-resistivity or nonselective sample with deterioration by the method that improves substrate temperature.
, present good crystalline texture, have low hillock occurrence probability, also have the occurrence probability of the local turmoil of low alloy lattice with direct heating device sedimentary Al-Si film in the hole.
Because aforesaid method is a kind of fabulous deposition method with regard to selectivity, therefore by again on the Al-Si of selective deposition film and above-mentioned SiO
2Use nonselective deposition method as the deposition method that continues on the isolated film, contain the metallic film of Al-Si, can obtain to be applicable to the metallic film of semiconducter device circuit as main ingredient and form.
The gas that contains element silicon is introduced by infeeding pipe 115, and it is the 3rd gas duct that enters mixing tank 104.
By using this film forming device, similar with the situation of pure Al, through heating 5 seconds or less time, can make the substrate surface temperature-stable in desired temperature.In addition, use this device can obtain high productive rate, even reach and per hour can handle 5 inches wafers of 15-30 sheet.
In another embodiment of the present invention, use multicell metal foil membrane formation device, at first, form in the chamber at the first film, use alkyl aluminium hydride and hydrogen according to the CVD method, on substrate, optionally form and contain the metallic film of Al, then substrate is transferred to second film and forms the chamber under the condition that is not exposed in the extraneous air, and on the whole surface of substrate, form metallic film as main ingredient.
According to the present invention, utilize the object lesson of the metallic film that multicell metal foil membrane formation device can form to comprise following combination: the pure Al of selective deposition and non-selective sedimentary pure Al, pure Al and Al-Si, pure Al and Al-Cu, pure Al and Al-Si-Cu, pure Al and Al-Ti etc.
In Al selective deposition process, preferable substrate surface temperature can be from alkyl aluminium hydride decomposition temp or higher temperature to being lower than 450 ℃, be more preferred from 260 ℃ to 440 ℃.
Particularly when using hydrogenation-aluminium trimethide (MMAH) and/or hydrogenation dimethyl aluminium (DMAH) also to use hydrogen as reactant gases as unstripped gas, and under the condition of the mixture of these gases, during the heated substrate surface, can form the second best in quality Al film with high sedimentation velocity.
In this case, when forming the Al film, the substrate surface temperature is more preferably remained on 260 ℃ to 440 ℃, then can be with than the second best in quality film of speed 3000-5000 dust higher under the resistive heating situation/minute obtain.
The object lesson of the metallic film that can form according to the present invention also can comprise following several combination: contain Al as main ingredient and contain as modifying element for example metal and the non-selective sedimentary Al of Al-Si etc., Al-Si and Al-Si, Al-Si and Al-Cu, Al-Si and Al-Si-Cu, Al-Si and Al-Ti, Al-Si and Al-Si-Ti etc.
When the Al-Si selective deposition, preferable substrate surface temperature be from the decomposition temperature of alkyl aluminium hydride or higher temperature to being lower than 450 ℃, be more preferred from 260 ℃ to 440 ℃.
Particularly work as and use hydrogenation monomethyl aluminium (MMAH) and/or hydrogenation dimethyl aluminium (DMAH), Si as unstripped gas
2H
6As the gas that contains modifying element, and hydrogen is as reactant gases, and during with lamp heated substrate surface, can form the second best in quality Al-Si film with high sedimentation velocity under the condition of the mixture of these gases.
In addition in the case, when the Al film forms, the substrate surface temperature is more preferably remained on 260 to 440 ℃, then can be with than the second best in quality film of speed 3000-5000 dust higher under the resistive heating situation/minute obtain.
The narration of metal foil membrane formation device (2)
The multicell device is another embodiment of preferable metal foil membrane formation device of the present invention.
Fig. 4 to Fig. 6 shows and can preferably implement metallic film of the present invention and form device continuously.
The metallic film of Fig. 4 forms device continuously and is made up of following part: material containing air lock 11, CVD reaction chamber (the first film formation chamber) 12, Rf etch chambers 13, sputtering chamber (second film forms the chamber) 14, material containing air lock 15, they with the continuously isolated condition of extraneous air under, the continuous and parallel configuration, and communicate with each other by slide valve 10, the formation of each chamber makes them be evacuated or to reduce pressure with pumped vacuum systems 16a-16e respectively.Above-mentioned material containing air lock 11 is used for using H after vacuumizing
2Atmosphere is done to replace the atmosphere of substrate to improve yield characteristics before the depositing treatment.The CVD reaction chamber 12 that continues is used for selective deposition on substrate under normal pressure or decompression, its internal equipment has base sheet rack 18, it has resistance heating body (being heated to 200 to 430 ℃) 17, and the formation of reaction chamber 12 also makes the gas that is used for CVD to introduce to carry out CVD by gas inlet tube 19.Rf etch chambers 13 then is used for carrying out after the selective deposition cleaning (soaking turbid) of substrate surface under Ar atmosphere, this chamber interior be equipped with base sheet rack 20 with to be heated to 100 ℃ to 250 ℃ and the electrode 21 that is used for the Rf etch, and infeed pipe 22 with Ar atmosphere and link to each other.The sputtering chamber 14 that is right after is used for carrying out nonselective depositing metal films by sputtering at substrate surface under Ar atmosphere, this chamber interior dispose base sheet rack 23 with to be heated to 200 ℃ to 250 ℃, and be used for thereon the fixedly target electroplax 24 of sputter target material 24a, and infeed pipe 25 with Ar gas and be connected.Last material containing air lock 1.5 is the watch-keeping cubicle when being fetched into substrate in the air after finishing deposit metal films, and it constitutes makes and can use N
2Replace wherein atmosphere.
In Fig. 4, it is to provide with time series on the basis of each step that the metallic film of above-mentioned formation forms device continuously.But be actually as shown in Figure 5, its formation is above-mentioned material containing air lock 11, CVD reaction chamber 12, and Rf etch chambers 13, sputtering chamber 14 and material containing air lock 15 are by linking together jointly as switch room 26.In this formation, the effect in material containing air lock 15 is also played in material containing air lock 11.As shown in the figure, in the isolated transfer chamber 26 of above-mentioned and air, be equipped with and on the BB of being rotated in direction capable of reversing on the AA direction, can move the arm of stretching (transport unit) 27.By means of arm 27, shown in the arrow of Fig. 6, substrate can move to CVD chamber 12, Rf etch chambers 13, sputtering chamber 14, material containing air lock 15 by material containing air lock 11 according to each step continuously successively under situation about not being exposed in the extraneous air.
Fig. 7 provided that metallic film forms device continuously another constitute example, and with Fig. 4 in identical member prosign mark.So the difference of the device of Fig. 7 and the device of Fig. 4 is on the surface with halogen lamp 30 direct heating substrates.In order to carry out direct heating, have one to be used for the nail 31 that support substrate makes it to be in suspended state on the base sheet rack 12.
Can be used in the heating unit of this method,, for example can comprise lamp heating method with halogen lamp, xenon lamp etc. as snead process (by transmitting energy heated substrate itself) by heating unit.In this connection, as resistive heating, heating unit that is equipped on the substrate supporting element etc. can be arranged, so that form deposit film thereon, supporting element is configured in the film formed space of deposition of thin this supporting element in order to support substrate.
Contain in deposition under the situation of aluminium film of modifying element, also may use the metal foil membrane formation device of Fig. 4 to Fig. 7 according to aforesaid method.
In brief, for introducing the gas except that organoaluminum gas, can add gas tube of assembling.
Below, the optional gas that is used for above-mentioned metal foil membrane formation device with reference to Fig. 9 narration infeeds system.
The gas introduction tube 312 of reaction chamber 301 links to each other with mixing tank 304.Many gas introduction tube links to each other with mixing tank 304, and wherein one is hydrogen ingress pipe 311, and it links to each other with water cooler 320.Another pipeline is a unstripped gas ingress pipe 312, and it links to each other with bubbler 305.Bubbler links to each other with vector gas ingress pipe 313 and is used for the foaming of liquid raw material, and this carrier gas ingress pipe 313 also is connected on the water cooler 320 similarly with pipe 311.
In addition, dispose hydrogen purification device 321 at inlet end by managing 327.
The preferably hydrogen purification device 321 of designs fix in the CVD apparatus main body, and to make the length of pipeline by purification cylinder 330 to CVD reaction chambers 312 be 1.5 meters or shorter.
Certainly, the connection portion of pipeline and valve is compressed to the shortest on demand.
This CVD device is installed in the indoor of cleaning, and the bomb 324 that holds raw hydrogen is configured in the cleaning chamber outside.The two communicates with each other with flue 325.These pipelines are made by the SUS through electropolishing.
Unstripped gas provides in the following manner by using said apparatus.Be heated to about 400 ℃ by the hydrogen that 10 meters or longer pipe 325 infeed preheater 323 at this by bomb 324.Heated raw hydrogen is purified by being heated to about 420 ℃ palladium.In brief, the purity of the hydrogen that exists in the jar 330 of purifying is 99.99995% or higher, and the hydrogen in the main chamber then has higher impurity concentration.At this, an amount of hydrogen makes that by delivery pipe 326 dischargings the impurity concentration in the hydrogen can unlikelyly become higher.
The hydrogen of purifying is through water cooler 320 coolings, and wherein a part is directly infeeded mixing tank 304, and the hydrogen that a part is used for bubbling infeeds bubbler 305.
The narration of metallic film formation method (2)
With reference to Fig. 2 and Fig. 4 in detail, another embodiment of metallic film formation method of the present invention is described in detail.
As described in above-mentioned (1), prepare the sedimentary substrate for the treatment of shown in Fig. 2 A.This substrate is placed the CVD reaction chamber shown in Fig. 4 12, and alkyl aluminium hydride gas and hydrogen are introduced by gas introduction tube 19.
By substrate temperature being remained on 260 ℃ to 440 ℃, be more preferred from 270 ℃ to 440 ℃, Al optionally deposits to (Fig. 2 B) in each hole.
Then, the substrate that will have the Al of selective deposition is being displaced downwardly among Fig. 4 in the 13 represented etch chambers with the isolated state of extraneous air, and its surface is by slight etch.Similarly, with the isolated state of extraneous air under, substrate is moved to reaction chamber 14, use sputtering method depositing metal films on whole substrate surface then, or the like (Fig. 2 C).
Sedimentary Al is single crystal structure in each hole according to the method described above, and it has fabulous characteristic, for example:
(1) reduced the occurrence probability of hillock;
(2) reduced the occurrence probability of the local turmoil of alloy lattice.
Aforesaid method is a kind of fabulous deposition method with regard to selectivity.By using non-selective deposition method, again at the Al of above-mentioned selective deposition film and SiO as follow-up deposition step
2Form on the insulating film and contain the metallic film of Al as main ingredient, or the like, so just can obtain to be applicable to the metallic film of semiconducter device circuit.
For Al-Si, also present fabulous crystal structure similarly.
Thereby the nonselective deposition method of general use is as the deposition step that continues, again at the Al-Si of above-mentioned selective deposition film and SiO
2Form Al on the insulating film or contain the metallic film of Al as main ingredient, or the like, so just can obtain to be applicable to the metallic film of semiconducter device circuit.
Thereby, according to the present invention improved in the hole Al and between the face of the Al on the insulating film characteristic, the result has obtained being used for the metallic film of circuit, can obtain enough low contact resistance with it.
Followingly describe with reference to embodiment.
At first narrate embodiment 1-9, wherein optionally form earlier pure Al film, be non-selectively formed then and contain the metallic film of Al as main ingredient, narrate embodiment 10-16 again, wherein optionally form earlier and contain for example Al film of Si etc. of a kind of element, be non-selectively formed then and contain the metallic film of Al as main ingredient.In addition, the metallic film formation method of Fig. 4 to device shown in Figure 7 used in narration with reference to embodiment 17-22.Here, the device among the embodiment 17-21 uses direct heating system (Fig. 7), and the device among the embodiment 22 uses resistive heating system (Fig. 4).
At first prepare substrate.This substrate is that having by the thickness that forms through thermooxidizing on N type single crystalline Si wafer is 8000 dust SiO
2Sample.This preparation process is by at SiO
2On manufacture and have 0.25 μ m * the square pattern of 0.25 μ m to the square different apertures of 100 μ m * 100 μ m, thereby expose the Si monocrystalline of bottom.Fig. 2 A has schematically represented the part of substrate.Wherein 1 is monocrystalline silicon substrate as semiconductor substrate, the 2nd, and as the silicon film of the thermooxidizing of insulating film.This is called as sample 1-1.VH1 and VH2 are the holes that diameter differs from one another.
Be described in the step that forms the Al film on the substrate 1 below.
Use device shown in Figure 1, reaction chamber 101 inside are evacuated to about 1 * 10 by pumped vacuum systems 107
-8Holder.Yet, both made vacuum tightness in the reaction chamber 101 than 1 * 10
-8It is poorer to hold in the palm, and the Al film also can form.
In this embodiment, DMAH is infeeded by first gas tube 111.Use H
2As vector gas by the DMAH pipe.
H
2Flowed by the second gas tube 111A, the pressure in the reaction chamber 101 then controls to preset value by controlling at a slow speed the opening degree of leak valve (not providing among the figure) with it.Generally pressure fixing is held in the palm about 1.5 in this embodiment.By DMAH pipeline 111 DMAH is introduced reaction tubes, about 1.5 holders of total pressure, and the pressure of DMAH about 5.0 * 10
-3Holder.The direct heating wafer of turning on light then, thereby depositing Al.
After through predetermined depositing time, stop to infeed DMAH immediately.The predetermined depositing time of sedimentary Al film is up at Si(monocrystalline silicon substrate 1 in this step) thickness of going up the Al film equals SiO
2Time during (silicon film 2 of thermooxidizing) film thickness.
This moment, the direct heating substrate surface made temperature maintenance at 270 ℃.Above-mentioned steps is called first deposition step.Till this step, shown in Fig. 2 B, Al film 3 optionally deposits in the hole.
Then, under the situation of not destroying vacuum, wafer is placed sputter equipment, again Al is deposited on SiO by sputter
2On the film 2.This step is nonselective deposition step.It is exactly so-called the 2nd Al thin film deposition steps.
The film formation condition of this moment is as described below.Using Al as target, is 10 at pressure
-1To 10
-3Apply 5 to 10kW direct supplys in the Ar atmosphere of holder and form film.Substrate temperature remained on 200 ℃ by resistive heating at that time.
According to the 2nd Al thin film deposition steps, shown in Fig. 2 C, can be at SiO
2Sedimentation velocity with 10000 dusts on the film 2 forms Al film 4.Formed the Al film according to the method described above.
In addition, by re-using the substrate of similar approach preparation, but this moment the substrate surface temperature is fixed on 280 ℃ to 480 ℃ through direct heating, prepares the Al film according to first deposition step.This other film formation condition that is in first deposition step and second deposition step is identical.
In addition, in first deposition step, form the Al film by the substrate surface temperature being fixed on 200 ℃ to 260 ℃ and 490 ℃ to 550 ℃.It the results are shown in table 1.
Table 1
Table 1(is continuous)
As can be seen from Table 1, make the substrate surface temperature under the situation of 260-440 ℃ of scope by direct heating, Al is with 3000-5000
/ minute sedimentation velocity optionally be deposited in the hole.
The substrate surface temperature is under the situation of 260-440 ℃ of scope, Al membrane property in the hole is tested, find that its characteristic is good, carbon containing not, resistivity is 2.8-3.4 μ Ω .cm, reflectivity is 90-95%, and 1 μ m or bigger hillock density are 0-10, does not have the local turmoil of lattice (spike) to produce (0.15 μ m is in conjunction with the destruction probability of (bonding)) basically.
Certainly, because the excellent surface characteristic of Al film under it finds that the Al film contact that sputter thereon forms is good.
On the contrary, be under 200 ℃ to 250 ℃ the situation in the substrate surface temperature, the low 1000-1500 that reaches of sedimentation velocity
/ minute, thereby output also be reduced to the 7-10 sheet/hour.
On the other hand, when the substrate surface temperature surpassed 440 ℃, reflectivity was 60% or littler, and 1 μ m or bigger hillock density are 10-10
4Cm
-2, the local turmoil of lattice is produced as 0-30%, thereby reduces the characteristic of Al film in the hole.
Subsequently, according to the method described above, has upward formation Al film of the substrate of following structure (sample).
On silicon single crystal,, make with lithography step body plan figure then to have the monocrystalline silicon surface that part exposes with the silicon oxide film of CVD method formation as the second substrate surface material as the first substrate surface material.
Thermooxidizing SiO
2The thickness of film is 7000
, the expose portion of silicon single crystal, promptly the hole is of a size of 2.5 μ m * 3 μ m to 10 μ m * 10 μ m.Preparation sample 1-2(hereinafter is expressed as " CVDSiO with this sample like this
2(hereinafter be abbreviated as SiO
2)/silicon single crystal ").
Sample 1-3 is boron-doping oxide film (hereinafter being abbreviated as the BSG)/silicon single crystal that forms with atmospheric pressure cvd,
Sample 1-4 is phosphorous doped oxide film (hereinafter being abbreviated as the PSG)/silicon single crystal that forms with atmospheric pressure cvd,
Sample 1-5 is the oxide film of mixing phosphorus and boron-doping (hereinafter being abbreviated as the BSPG)/silicon single crystal that forms with atmospheric pressure cvd,
Sample 1-6 is nitride film (hereinafter being abbreviated as the P-SiN)/silicon single crystal that forms with plasma CVD,
Sample 1-7 is hot nitrided film (hereinafter being abbreviated as T-SiN)/silicon single crystal,
Sample 1-8 is nitrided film (hereinafter being abbreviated as the LP-SiN)/silicon single crystal that forms with low voltage DC VD, and
Sample 1-9 is nitrided film (hereinafter being abbreviated as the ECR-SiN)/silicon single crystal that forms with the ECR device.In addition, according to the first substrate surface material shown in hereinafter and all combinations of the second substrate surface material, preparation sample 1-11 to 1-179.Adopt as the first substrate surface material: silicon single crystal (single silicon Si), polysilicon (polycrystalline Si), non-crystalline silicon (amorphous Si), tungsten (W), molybdenum (Mo), tantalum (Ta), tungsten silicide WSi), titanium silicide (TiSi), aluminium (Al), aluminium silicon (Al-Si), titanium aluminium (Al-Ti), titanium nitride (Ti-N), copper (Cu), aluminium copper silicon (Al-Si-Cu), aluminium palladium (Al-Pd), titanium (Ti), molybdenum silicide (Mo-Si), tantalum silicide (Ta-Si).Adopt as the second substrate surface material: T-SiO
2, SiO
2, BSG, PSG, BPSG, P-SiN, T-SiN, LP-SiN, ECR-SiN.Above-mentioned all samples all can form good Al film.
By carrying out an Al deposition step identical, use CVD method as the trimethyl aluminium (TMA) of second deposition step on whole surface, to form the Al film then and finish embodiment 2 with embodiment 1.Preparation and (the sample 1-1) that use in embodiment 1 have the substrate of same structure.According to an above-mentioned Al deposition step, in the hole the substrate rest of depositing Al in the CVD device.
Use trimethyl aluminium (TMA) as unstripped gas, at TMA and H
2Form the Al film at whole substrate surface in the mixed atmosphere of gas.
According to second deposition step of present embodiment, with 500
/ minute sedimentation velocity depositing Al film, the transfer resistance of film is fabulous, and resistivity is 3.3-3.5 μ Ω .cm.
In the embodiment of the invention 3, use the device shown in Fig. 1, DMAH is as unstripped gas, and hydrogen is as reactant gases, and forms aluminium (Al) film with halogen lamp direct heating substrate surface.
Similar monocrystalline silicon piece is as substrate among preparation and the embodiment 1, and covering has the square SiO to the square hole of 100 μ m of many 0.25 μ m on it
2Film.To this substrate, as described below, carry out an Al film deposition step and carry out the 2nd Al-Si film deposition step and form the Al film with the CVD method with sputtering method.
With the processing method identical, DMAH and hydrogen is transported to carries out the Al deposition in the reaction chamber 101 with embodiment 1.
The condition that the one Al film forms step is stagnation pressure 1.5 torrs, DMAH dividing potential drop 1.5 * 10
-4Torr, 270 ℃ of substrate surface temperature.
With an above-mentioned Al deposition step, with 3000-5000
/ minute sedimentation velocity Al is deposited to the selectivity to obtain in the hole in various apertures.Subsequently, in sputter equipment, Al-Si is comprising SiO substrate rest
2With deposit to 5000 on the whole surface of selective deposition Al
Thickness.At this moment sedimentation velocity is 10000
/ minute.
In addition, with identical method, use with embodiment 1 in identical sample 1-11 to 1-179 as substrate formation Al film.In all samples, the Al film that can form through first and second deposition steps.
In above-mentioned experiment, the substrate surface temperature is 270 ℃, but this condition is to change to 550 ℃ to form the Al film every 10 ℃ from 200 ℃.
With an Al deposition step, the property class of the Al film of aforesaid each sample is similar to shown in the table 1.
Embodiment 4
In embodiment 4, after finishing an Al deposition step identical with embodiment 1, the CVD method of the use TMA by being used as second deposition step forms the Al-Si film on whole surface.
(the sample 1-1) that uses among preparation and the embodiment 1 has the substrate of same structure.
Amassing the substrate rest of Al in the CVD device at inner hole deposition with an above-mentioned Al deposition step.
Use Si
2H
5And trimethyl aluminium (TMA) is as unstripped gas, in the mixed atmosphere of itself and hydrogen on whole substrate surface depositing Al-Si film.
With second deposition step of present embodiment, with 500
/ minute sedimentation velocity depositing Al-Si film, the transfer resistance of film is fabulous, and resistivity is 3.3-3.5 μ Ω .cm.
Embodiment 5
In embodiment 5, after finishing an Al deposition step identical, use as forming the Al-Cu film on the whole substrate surface of sputtering at of second deposition step with embodiment 1.(the sample 1-1) that uses among preparation and the embodiment 1 has the substrate of same structure.
With an above-mentioned Al deposition step optionally behind the long-pending Al of inner hole deposition, substrate rest in sputter equipment.The film formation condition is as described below in sputter procedure.
Use Al-Cu(0.5%) as target, 5 * 10
-3The DC power supply that uses in the Ar atmosphere of torr is 7KW.
With second deposition step of present embodiment, with 10000
/ minute sedimentation velocity depositing Al-Cu film, the transfer resistance of film is fabulous, and resistivity is 3.0-3.3 μ Ω .cm.
Embodiment 6
In embodiment 6, after finishing an Al deposition step identical, be used as the use TMA and the bis-acetylacetonate acid copper Cu(C of second deposition step with embodiment 1
5H
7O
2)
2The CVD method form the Al-Cu film.
Preparation and (the sample 1-1) that use in embodiment 1 have the substrate of same structure.
With an above-mentioned Al deposition step optionally behind the long-pending Al of inner hole deposition, substrate rest in the CVD device.
Use TMA and conduct to contain the Cu(C of Cu gas
5H
7O
2)
2As unstripped gas, depositing Al on whole substrate surface-Cu film.
With second deposition step of present embodiment, with 500
/ minute sedimentation velocity depositing Al-Cu film, the transfer resistance of film is fabulous, and resistivity is 3.3-3.5 μ Ω .cm.
Embodiment 7
In embodiment 7, after finishing an Al deposition step identical, on whole substrate surface, form the Al-Si-Cu film as second deposition step with sputter with embodiment 1.(the sample 1-1) that uses among preparation and the embodiment 1 has the substrate of same structure.
With an above-mentioned Al deposition step optionally behind the long-pending Al of inner hole deposition, substrate rest in sputter equipment.The film formation condition is as follows in sputter procedure.Use Al-Si(0.5%)-Cu(0.5%) as target, the DC power supply that uses in Ar atmosphere is 7KW.
With second deposition step of present embodiment, with 10000
/ minute sedimentation velocity depositing Al-Si-Cu film, the transfer resistance of film is fabulous, and resistivity is 3.0-3.3 μ Ω .cm.
Preparation and (the sample 1-1) that use in embodiment 1 have the substrate of same structure.With an above-mentioned Al deposition step optionally behind the long-pending Al of inner hole deposition, substrate rest in the CVD device.Use as the Si that contains Si gas
2H
6, TMA and as containing the Cu(C of Cu gas
5H
7O
2)
2As unstripped gas, depositing Al on whole substrate surface-Si-Cu film.
With second deposition step of present embodiment, with 500
/ minute sedimentation velocity depositing Al-Si-Cu film, the transfer resistance of film is fabulous, and resistivity is 3.3-3.5 μ Ω .cm.
Embodiment 9
Embodiment 9 shows is after finishing an Al deposition step identical with embodiment 1, forms the Al-Ti film as second deposition step with sputter on whole substrate surface.Preparation and (the sample 1-1) that use in embodiment 1 have the substrate of same structure.
With an above-mentioned Al deposition step optionally behind the long-pending Al of inner hole deposition, substrate rest in sputter equipment.
The film formation condition is as follows in sputter procedure.Use Al-Ti(0.5%) as target, the DC power supply that uses in Ar atmosphere is 7KW.
With second deposition step of present embodiment, with 10000
/ minute sedimentation velocity depositing Al-Ti film, the transfer resistance of film is fabulous, and resistivity is 3.0-3.3 μ Ω .cm.
Having narrated embodiment 1-9 above, similarly, also is possible in the first deposition step depositing Al and in second step with CVD method depositing Al-Ti.Also is possible in the first step depositing Al and in second step with sputtering method or CVD method depositing Al-Si-Ti.
Contrast experiment's example 1
Use CVD device shown in Figure 3, preparation and (the sample 1-1 to 1-179) that use in embodiment 1 have the substrate of same structure, and experiment is heated by resistive, indirect heating substrate under the wide temperature condition from 200 ℃ to 650 ℃.
As a result, although all deposited the fabulous Al of selectivity in the hole in all samples, the sedimentation velocity of this moment is 100-800
/ minute, compare approximately low one-bit digital with the various embodiments described above.
Among Fig. 3, the 11st, reaction chamber, the 12nd, well heater, the 13rd, support, the 14th, mixing tank, the 15th, bubbler, the 16th, the gas entrance hole, the 17th, evacuation system, the 18th, evacuation holes, the 19th, substrate, the 20th, gas introduction tube, the 21st, the gas of DMAH gas feeds pipe, and 21A is H
2Gas feeds pipe, and 22 is evacuation tube.
In the foregoing description 1-9, because optionally substrate is by direct heating in the deposition of aluminum process on substrate, so the result can form the fabulous metallic membrane of membrane property with high sedimentation velocity.
At first prepare substrate.Substrate is that the thickness that forms by thermooxidizing on N type single-chip is 8000
SiO
2Sample.Obtaining it is at SiO
2Last manufactured size is that 0.25 μ m * 0.25 μ m is square to 100 μ m * square various perforates of 100 μ m, thus the Si monocrystalline under exposing.Fig. 2 A illustrates the part of substrate.Wherein, the 1st, as the monocrystalline silicon substrate of semiconductor substrate, the 2nd, as the thermal oxidation silicon film of insulating film.Claim that it is sample 1-1.VH
1And VH
2Be mutual different hole, aperture.
The processing method that forms the Al-Si film on substrate 1 is as follows.
Use device shown in Figure 1, with evacuation system 107 reaction chamber 101 inner pumpings extremely about 1 * 10
-8Torr.Yet, both made the vacuum tightness in the reaction chamber 101 be higher than 1 * 10
-8Torr also can form the Al-Si film.
In the present embodiment, DMAH feeds from first flue 111, simultaneously Si
2H
6Feed from the 3rd flue 115.Use H
2As vector gas by the DMAH pipe.
H
2Flow through by the second flue 111A, the hole of leak valve (not providing among the figure) controls to preset value to reaction chamber 101 pressure inside by controlling at a slow speed.Typical pressure is about 1.5 torrs in the present embodiment.By DMAH pipe 111 DMAH is imported reaction chamber.About 1.5 torrs of stagnation pressure, the DMAH dividing potential drop is about 1.5 * 10
-4Torr, Si
2H
6Dividing potential drop is 2 * 10
-6Then, the direct heating wafer of turning on light.Depositing Al-Si like this.
In forming the Al-Si membrane process, can be used as the Si that has that second unstripped gas that contains Si uses
2H
6, SiH
4, Si
3H
8, Si(CH
3)
4, SiCl
4, SiH
2Cl
2, SiH
3Cl.
By adding DMAH, H
2With Si unstripped gas, such as Si
2H
6Can deposit the Al-Si that contains 0.5-2.0%Si.Reaction tubes pressure is the 0.05-760 torr, wishes the torr for 0.1-0.8, and substrate temperature is 260 ℃ to 440 ℃, and the DMAH dividing potential drop is 1 * 10 of a reaction tubes internal pressure
-5Doubly to 1.3 * 10
-3Doubly, Si in the reaction tubes
2H
6Dividing potential drop is 1 * 10
-7To 1 * 10
-4Times, thereby depositing Al-Si.
After through predetermined depositing time, just stop to feed of DMAH.The predetermined depositing time of depositing Al film is up at Si(monocrystalline silicon substrate i in this step) go up film Al-Si film thickness and equal SiO
2The time of (thermal oxidation silicon film 2) film thickness.
Be 270 ℃ by direct-fired substrate surface temperature this moment.Above-mentioned steps is called first deposition step.With step so far, shown in Fig. 2 B, Al-Si film 3 optionally is deposited in the hole.
Subsequently, wafer is placed in the sputter equipment, Al-Si also is deposited on SiO like this
2On the film 2.This step is non-selective deposition step.This is called the 2nd Al-Si film deposition step.
The film formation condition of this moment is as described below.Use Al-Si as target, warp is 10 at pressure
-1-10
-3Use the DC power supply of 5-10KW in the Ar atmosphere of torr and form film.It is 200 ℃ that the method that is heated by resistive this moment makes substrate temperature.
Shown in Fig. 2 (C), with the 2nd Al-Si film deposition step, with 10000
/ minute sedimentation velocity is at SiO
2Can form Al-Si film 4 on the film 2.Form the Al-Si film with aforesaid method.
In addition, reusing the substrate of similar preparation, is 280 ℃ to 480 ℃ but make the substrate surface temperature of this moment with direct heating, prepares the Al-Si film with first deposition step.Here, the film formation condition of the film shape of other first deposition step or condition and second deposition step is all identical.
Similarly, in the first deposition step process, make the substrate surface temperature be 200 ℃ to 260 ℃ and 490 ℃ to 550 ℃ and form the Al-Si film.Find in result and the aforementioned table 1 identical.
As what can find out, when making the substrate surface temperature be 260-440 ℃, with 3000-5000 by direct heating from table 1
/ minute sedimentation velocity Al-Si optionally is deposited in the hole.
Under substrate temperature is the situation of 260-440 ℃ of scope, the characteristic of the Al-Si film in the hole is tested, find that its characteristic is good, carbon containing not, resistivity is 2.8-3.4 μ Ω .cm, reflectivity is 90-95%, 1 μ m or higher hillock density are 0-10, do not have the local turmoil of lattice to produce (0.15 μ m bonded destroys probability) basically.
Certainly, because the excellent surface characteristic of the Al-Si film under it, it is good finding to contact with the Al film that forms thereon by sputter.
On the contrary, be under 200 ℃-250 ℃ the situation in the substrate surface temperature, the low 1000-1500 that reaches of sedimentation velocity
/ minute, thereby output also be reduced to the 7-10 sheet/hour.
On the other hand, when the substrate surface temperature surpassed 440 ℃, reflectivity was 60% or littler, and 1 μ m or bigger hillock density are 10-10
-4Cm
-2, the local turmoil of lattice is produced as 0-30%, thereby has reduced the characteristic of Al-Si film in the hole.
Subsequently, use aforesaid method, have upward formation Al-Si film of the substrate of following structure (sample).
On silicon single crystal,, with lithography step body plan figure monocrystalline silicon surface is partly exposed then with the silicon oxide film of CVD method formation as the second substrate surface material as the first substrate surface material.
Thermooxidizing SiO
2The thickness of film is 7000
, the expose portion of silicon single crystal, promptly the hole is of a size of 2.5 μ m * 3 μ m to 10 μ m * 10 μ m.Preparation sample 1-2(hereinafter is expressed as " CVDSiO with this sample like this
2(hereinafter be abbreviated as SiO
2)/silicon single crystal ").
Sample 1-3 is boron-doping oxide film (hereinafter being abbreviated as the BSG)/silicon single crystal that forms with atmospheric pressure cvd,
Sample 1-4 is phosphorous doped oxide film (hereinafter being abbreviated as the PSG)/silicon single crystal that forms with atmospheric pressure cvd,
Sample 1-5 is the oxide film of mixing phosphorus and boron-doping (hereinafter being abbreviated as the BSPG)/silicon single crystal that forms with atmospheric pressure cvd,
Sample 1-6 is nitride film (hereinafter being abbreviated as the P-SiN)/silicon single crystal that forms with plasma CVD,
Sample 1-7 is hot nitrided film (hereinafter being abbreviated as T-SiN)/silicon single crystal,
Sample 1-8 is nitrided film (hereinafter being abbreviated as the LP-SiN)/silicon single crystal that forms with low voltage DC VD, and
Sample 1-9 is nitrided film (hereinafter being abbreviated as the ECR-SiN)/silicon single crystal that forms with the ECR device.In addition, with all combinations of the first substrate surface material shown in following and the second substrate surface material, preparation sample 1-11 to 1-179.Use as the first substrate surface material: silicon single crystal (single crystalline Si), polysilicon (polycrystalline Si), non-crystalline silicon (amorphous Si), tungsten (W), molybdenum (Mo), tantalum (Ta), tungsten silicide (WSi), titanium silicide (TiSi), aluminium (Al), aluminium silicon (Al-Si), titanium aluminium (Al-Ti), titanium nitride (Ti-N), copper (Cu), aluminium copper silicon (Al-Si-Cu), aluminium palladium (Al-Pd), titanium (Ti), molybdenum silicide (Mo-Si), tantalum silicide (Ta-Si).Use as the second substrate surface material: T-SiO
2, SiO
2, BSG, PSG, BPSG, P-SiN, T-SiN, LP-SiN, ECR-SiN.Above-mentioned all samples all can form good Al film.
By carrying out an Al-Si deposition step identical with embodiment 10, the CVD method through using trimethyl aluminium (TMA) forms the Al-Si film as second deposition step and finishes embodiment 11 on whole surface then.Preparation and (the sample 1-1) that use in embodiment 10 have the substrate of same structure.With an above-mentioned Al-Si deposition step, amassing the substrate rest of Al-Si in the CVD device at inner hole deposition.
Use trimethyl aluminium (TMA) as unstripped gas, with H
2Form the Al-Si film at whole substrate surface in the mixed atmosphere of gas.
With second deposition step of present embodiment, with 500
/ minute sedimentation velocity depositing Al-Si film, the transfer resistance of film is fabulous, and resistivity is 3.3-3.5 μ Ω .cm.
With an above-mentioned Al-Si deposition step optionally behind the long-pending Al-Si of inner hole deposition, substrate rest in sputter equipment.The film formation condition is as described below in the sputter procedure.
Use Al-Cu(0.5%) as target, 5 * 10
-3The DC power supply that uses in the Ar atmosphere of torr is 7KW.
With second deposition step of present embodiment, with 10000
/ minute sedimentation velocity depositing Al-Cu film, the transfer resistance of film is fabulous, and resistivity is 3.0-3.3 μ Ω .cm.
Preparation and (the sample 1-1) that use in embodiment 10 have the substrate of same structure.
With an above-mentioned Al-Si deposition step optionally behind the long-pending Al of inner hole deposition, substrate rest in the CVD device.
Make unstripped gas with TMA, Cu(C
5H
7O
2)
2Work contains Cu gas, and on whole substrate surface depositing Al-Cu film.
Second deposition step of present embodiment is with 500
The sedimentation velocity of/min is come depositing Al-Cu film, and this film is the fabulous film of a kind of transfer resistance (migration resistance), and its resistivity is 3.3-3.5 μ Ω .cm.
What embodiment 14 was indicated is, behind the same Al-Si deposition step, presses sputtering method and form the Al-Si-Cu film on whole substrate surface, as second deposition step in finishing with embodiment 10.Substrate preparation becomes to have same spline structure with substrate for use among the embodiment 10 (sample 1-1).
By an above-mentioned Al-Si deposition step, be chosen in the hole behind depositing Al-Si, substrate is placed in the sputter equipment.During sputter, the formation condition of film is as follows.Use Al-Si(0.5%) make target, and to make DC power in Ar atmosphere be 7KW.
Second deposition step in the present embodiment is with 10000
The sedimentation velocity of/min is come depositing Al-Si-Cu film, and this film is the good film of a kind of transfer resistance, and its resistivity is 3.0-3.3 μ Ω .cm.
What embodiment 15 was indicated is, behind the same Al deposition step, uses bis-acetylacetonate acid copper Cu(C in finishing with embodiment 10
5H
7O
2)
2, H
2And Si
2H
6, form the Al-Si-Cu film by the CVD method.
Substrate (sample 1-1) used among 44 substrate preparation one-tenth and the embodiment 10 has same spline structure.By an above-mentioned Al-Si deposition step, be chosen in the hole behind depositing Al-Si, substrate is placed in the CVD device.Make unstripped gas with TMA, Si
2H
6Work contains Si gas, and Cu(C
5H
7O
2)
2Work contains Cu gas, and the Al-Si-Cu film is deposited on the whole substrate surface.
Second deposition step of present embodiment is with 500
The sedimentation velocity of/min is come depositing Al-Si-Cu film, and this film is the good film of transfer resistance, and its resistivity is 3.3-3.5 μ Ω .cm.
Embodiment 16
What embodiment 16 was indicated is, behind the same Al-Si deposition step, presses sputtering method and form the Al-Ti film on whole substrate surface, as second deposition step in finishing with embodiment 10.Substrate preparation becomes to have the same structure with substrate for use among the embodiment 10 (sample 1-1).
By an above-mentioned Al-Si deposition step, be chosen in the hole behind depositing Al-Si, substrate is placed in the sputter equipment.
During sputter, the formation condition of film is as follows.Target adopts Al-Ti(0.5%), DC power is 7KW in the Ar atmosphere.
Second deposition step in the present embodiment is with 10000
Sedimentation velocity depositing Al-Ti film of/min, this film are the good films of a kind of transfer resistance, and its resistivity is 3.0-3.3 μ Ω .cm.
Embodiment 10-16 is illustrated above.In addition, depositing Al-Si in first deposition step, and in second step, press CVD method depositing Al-Ti, this also is feasible.Depositing Al-Si in first step, and in second step, press sputtering method or CVD method depositing Al-Si-Ti, also possible.
Comparative experimental example 2
Use CVD device shown in Figure 3, the substrate (sample 1-1 to 1-179) that preparation has substrate for use structure among the embodiment 10 under 200-650 ℃ of wide temperature range condition, is tested with the resistance indirect heating.
As a result, be deposited in the hole of all samples although have good optionally Al-Si, sedimentation velocity at that time is 100-800
/ min compares with the various embodiments described above, poor approximately one digit number.
Among Fig. 3, the 11st, reaction chamber, the 12nd, well heater, the 13rd, support, the 14th, mixing tank, the 15th, bubbler, the 16th, gas is introduced hole, the 17th, evacuation system, the 18th, evacuation holes, the 19th, substrate, the 20th, gas is introduced conduit, and the 21st, supply with the gas supply pipe that DMAH gas is used, 21A supplies with H
2The gas supply pipe that gas is used, the 22nd, the conduit of finding time.
In the foregoing description 10-16, because on substrate selectively during deposition of aluminum, substrate is by direct heating, so the result is to form the metallic membrane with good membranes characteristic with high sedimentation velocity.
At first prepare substrate.Substrate is to have through thermooxidizing on the N type single-chip to form 8000
Thickness SiO
2Sample.At SiO
2The square sectional hole patterns of last printing 0.25 μ m * 0.25 μ m to 100 μ m * square different size of 100 μ m.Si monocrystalline under making is exposed, makes sample with this.Fig. 2 A illustrates the part of substrate with synoptic diagram.Wherein, the 1st, as the monocrystalline silicon substrate of semiconductor substrate, the 2nd, as the thermal oxidation silicon film of insulating film (layer).This substrate is called sample 1-1.VH1 and VH2 are hole (exposed parts), and their aperture is different.
The method that forms the Al film on substrate is as follows.
At first, substrate 1 is placed in the material containing air lock 11.As mentioned above, hydrogen is introduced in the material containing air lock 11, it is under the nitrogen atmosphere.With evacuation system 10 reaction chamber 12 inner pumpings are arrived about 1 * 10
-2Holder.
But, even the vacuum tightness in the reaction chamber 12 is higher than 1 * 10
-8Holder also can form the Al film.
DMAH is imported by unshowned gas duct.Use H
2As carrier gas by the DMAH conduit.
Transport of reactant gases body H in unshowned second gas duct
2And establish, and the pressure in the reaction chamber 12 by the unshowned opening degree of letting out valve slowly of control, is controlled in preset value.In this case, be about 1.5 holders generally with pressure.DMAH is introduced into reaction chamber by the DMAH conduit.Total pressure is about 1.5 holders, and the dividing potential drop of DMAH is about 5.0 * 10
-3Holder.Then, make electric current pass through resistance heat producing element 17 on the base sheet rack 18, with the direct heating wafer.Like this, Al just is deposited up.
Predetermined depositing time one mistake is promptly stopped for DMAH.The predetermined depositing time of institute's depositing Al film in this step is a Si(monocrystalline silicon substrate 1) on the Al film thickness become and equal SiO
2Time during film (thermal oxidation silicon film 2) thickness.
At this moment, making direct-fired substrate surface temperature is 270 ℃.Above-mentioned steps is called first deposition step.According to the step of so far having stated, Al film 3 is selected to be deposited in the hole shown in Fig. 2 B.
After finishing above-mentioned Al deposition, CVD reaction chamber 12 is found time, reach 5 * 10 up to vacuum tightness with evacuation system 10
-3Till the holder.Simultaneously, Rf etching chamber 13 is evacuated to 5 * 10
-6Holder or low value more.Prove conclusively after two Room all reach above-mentioned vacuum tightness, open gate valve 10, utilize transporting mechanism (arm) 27, substrate is moved on to Rf etching chamber 13 from CVD reaction chamber 12, and closing gate valve 10.
When substrate is sent to Rf etching chamber 13, with evacuation system 10 Rf etching chamber 13 is found time, reach 10 up to vacuum tightness
-6Holder or more till the low value.
Then, for the purpose of carrying out the Rf etching, argon gas is fed to argon gas feed conduit 22, and Rf etching chamber 13 is remained on 10
-1To 10
-3Under the argon atmospher of holder.The base sheet rack 20 that the Rf etching is used maintains 200 ℃.In order to carry out etching, 100W Rf is supplied with Rf etching electrode 21, last 60 seconds, with this argon is discharged in Rf etching chamber 13, come the etching substrate surface with argon ion, remove the upper layer of CVD deposited film.In the case, etching depth is equivalent to oxidated layer thickness, is about 100
In the above explanation of doing, the surface etch of CVD deposited film is carried out in the Rf etching chamber.But, because the cvd film upper layer is defeated through vacuum and oxygen-free etc. on the substrate, so do not carry out etching.Under the sort of situation, when the temperature difference was big between CVD reaction chamber 12 and the sputtering chamber 14, Rf etching chamber 13 just played the temperature-changing chamber effect that changes temperature at short notice.
In Rf etching chamber 13, finish the Rf etching after, make argon gas stop to flow into, and the argon gas in the Rf etching chamber 13 found time.Be evacuated to 5 * 10 at Rf etching chamber 13
-6Holder, and sputtering chamber 14 is evacuated to 5 * 10
-6 Gate valve 10 is opened in holder or more after the low value.Then, by means of arm 27, substrate is moved on to sputtering chamber 14 from Rf etching chamber 13, closing gate valve 10 subsequently.
When substrate is transported to sputtering chamber 14, similar in Rf etching chamber 13 like that, with base sheet rack 23 10
-1-10
-3Under the argon atmospher of holder, be adjusted to 250 ℃.
In the present embodiment, argon discharge is carried out under DC power 7KW, so that with argon ion scraping target material Al-Si(0.5%), thereby with 10000
The sedimentation velocity of/min is deposited on Al-Si on the substrate.This step is non-selective deposition step.
This step is called the 2nd Al film deposition step.
Deposit 5000 on the substrate
Behind the Al film, make argon gas stop to flow into, and stop power for DC.With material containing air lock 11(15) be evacuated to 5 * 10
-3Or more behind the low value, open gate valve 10, shift out substrate.Behind the closing gate valve 10, make N
2Gas flows into material containing air lock 11(15), after reaching normal atmosphere, substrate is moved on to the device outside through gate valve 10.
Film formation condition in above-mentioned the 2nd Al film deposition step is as described below.Making target with Al, is 10 at pressure
-1To 10
-3Under the argon atmospher of holder, supply with the DC power of 5-10KW and form this film.At that time, make substrate temperature reach 200 ℃ through resistive heating.
By above-mentioned the 2nd Al film deposition step, can be at SiO
2On the film 2, with 10000
The sedimentation velocity of/min forms the Al film 4 shown in Fig. 2 C.The Al film forms as stated above.
In addition, still using by the substrate with the quadrat method preparation, is 280-480 ℃ but make the substrate surface temperature through direct heating this moment, prepares the Al film with this by first deposition step.At this moment, other film formation condition is all the same with film formation condition in second deposition step in first deposition step.
Equally, also in first deposition step, the substrate surface temperature regulation is formed the Al film at 200-260 ℃ and 490-550 ℃.The result is identical with person shown in the previous table 1.
As can be seen from Table 1, make the substrate surface temperature when 260 ℃ change to 440 ℃ with snead process, Al is with 3000-5000
The sedimentation velocity of/min is chosen in the hole and deposits.
The substrate surface temperature is when 260 ℃ change to 440 ℃, the assay of Al membrane property is good in the hole, carbon containing not in the film, resistivity is 2.8-3.4 μ Ω .cm, reflectivity is 90-95%, the density of 1 μ m or higher hillock is 0-10, and the local turmoil of essentially no lattice takes place by (0.15 μ m bonded destroys probability).
Certainly, because the Al film under it has the excellent surface characteristic, so, also be good with the intermembranous contact of Al that forms thereon with sputtering method.
By contrast, when the substrate surface temperature was 200-250 ℃, sedimentation velocity was low to 1000-1500
/ min, thus output also drop to the 7-10 sheet/hour.
On the other hand, when the substrate surface temperature surpassed 440 ℃, reflectivity was 60% or lower, and the density of 1 μ m or higher hillock is 10-10
4Cm
-2, the incidence of the local turmoil of lattice is 0-30%, thereby, the characteristic variation of Al film in the hole.
Next step as stated above, has upward formation Al film of the substrate of following structure (sample).
On silicon single crystal, press the CVD method and form silicon oxide film, as the second substrate surface material as the first substrate surface material.Then, by each lithography step printing figures, make monocrystalline silicon surface partly exposed.
Thermooxidizing SiO
2The thickness of film is 7000
, the silicon single crystal exposed part, promptly the hole is of a size of 0.25 μ m * 0.25 μ m to 10 μ m * 10 μ m.It is following with " CVD SiO like this, just to make this sample of sample 1-2(
2(below write a Chinese character in simplified form into SiO
2)/silicon single crystal " expression).
Sample 1-3 with the atmospheric pressure cvd method form, the oxide film of doped with boron (below write a Chinese character in simplified form into BSG)/silicon single crystal;
Sample 1-4 with the atmospheric pressure cvd method form, the oxide film of Doping Phosphorus (below write a Chinese character in simplified form into PSG)/silicon single crystal;
Sample 1-5 with the atmospheric pressure cvd method form, the oxide film of Doping Phosphorus and boron (below write a Chinese character in simplified form into BSPG)/silicon single crystal;
Sample 1-6 is the nitrided film that forms with plasma CVD method (below be called P-SiN)/silicon single crystal;
Sample 1-7 is hot nitrided film (below write a Chinese character in simplified form into T-SiN)/silicon single crystal;
Sample 1-8 is the nitrided film that forms with low voltage DC VD method (below write a Chinese character in simplified form into LP-SiN)/silicon single crystal; And
Sample 1-9 is the nitrided film that forms with the ECR device (below write a Chinese character in simplified form into ECR-SiN)/silicon single crystal.In addition, all combinations according to the first substrate surface material shown in following and the second substrate surface material have prepared sample 1-11 to 1-179.The first substrate surface material adopts silicon single crystal (single crystalline Si), polysilicon (polycrystalline Si), non-crystalline silicon (amorphous Si), tungsten (W), molybdenum (Mo), tantalum (Ta), tungsten silicide (WSi), titanium silicide (TiSi), aluminium (Al), aluminium silicon (Al-Si), titanium aluminium (Al-Ti), titanium nitride (Ti-N), copper (Cu), aluminium copper silicon (Al-Si-Cu), aluminium-palladium (Al-Pd, titanium (Ti), molybdenum silicide (Mo-Si), tantalum silicide (Ta-Si).That use as the second substrate surface material is T-SiO
2, SiO
2, BSG, PSG, BPSG, P-SiN, T-SiN, LP-SiN, ECR-SiN.To above-mentioned all samples, all can form good Al film.
What the embodiment of the invention 18 was indicated is, with the device shown in Fig. 7, makes unstripped gas with DMAH, and hydrogen is made reactant gases, forms the Al film with halogen lamp 30 direct heating substrate surfaces.
Press the same quadrat method among the embodiment 17, DMAH and hydrogen are transported to carry out the sedimentary CVD reaction chamber 12 of Al.
The condition that the one Al film forms step is total pressure 1.5 holders, DMAH dividing potential drop 1.5 * 10
-4Holder, 270 ℃ of substrate surface temperature.
An above-mentioned Al deposition step is with 3000-5000
The sedimentation velocity of/min, depositing Al in the hole in different apertures, thus can obtain good selectivity.Then, substrate is placed in the sputtering chamber 14, is containing SiO
2Whole surface on depositing Al-Si to 5000
Thick, and depositing Al selectively.Sedimentation velocity at that time is 10000
/ min.
In addition, in the same way, use as substrate, forms the Al film with sample 1-11 to 1-179 the same among the embodiment 17.In all samples,, can form good Al film by first and second deposition steps.
In above-mentioned each test, the substrate surface temperature is transferred to 270 ℃, and forms the Al film from 200 ℃ to 550 ℃ every 10 ℃ of these conditions of change.
All relevant samples are according to the sedimentary Al film of an Al deposition step, and its characteristic all is similar to the characteristic shown in the table 1.
What embodiment 19 was indicated is, after finishing an Al deposition step identical with embodiment 17, as second deposition step, forms the Al-Cu film with sputter on whole substrate surface.Substrate preparation becomes to have same structure with (sample 1-1) used among the embodiment 17.
By an above-mentioned Al deposition step, in the hole, after the depositing Al, substrate is placed in the sputter equipment 14 selectively.Film formation condition during sputter is as described below.
Use Al-Cu(0.5%) make target, 5 * 10
-3Making DC power in the argon atmospher of holder is 7KW.
Second deposition step in the present embodiment is with 10000
Sedimentation velocity depositing Al-Cu film of/min, this film are the good films of transfer resistance, and its resistivity is 3.0-3.3 μ Ω .cm.
In embodiment 20, through finish with embodiment 17 in behind the identical Al deposition step, press sputtering method and on whole substrate surface, form the Al-Si-Cu film, with this as second deposition step.Substrate (sample 1-1) used among substrate preparation one-tenth and the embodiment 17 has same spline structure.
By an above-mentioned Al-Si deposition step, be chosen in the hole after the depositing Al, substrate is placed in the sputtering chamber 14.During sputter, the formation condition of film is as follows.Use Al-Si(0.5%)-Cu(0.5%) make target, making DC power in Ar atmosphere is 7KW.
Second deposition step in the present embodiment is with 10000
Sedimentation velocity depositing Al-Si-Cu film of/min, this film are the good films of transfer resistance, and its resistivity is 3.0-3.3 μ Ω .cm.
In embodiment 21, after finishing an Al deposition step identical, press sputtering method and on whole substrate surface, form the Al-Ti film, as second deposition step with embodiment 17.Substrate for use (sample 1-1) has same structure among substrate preparation one-tenth and the embodiment 17.
By an above-mentioned Al deposition step, be chosen in the hole after the depositing Al, substrate is placed in the sputtering chamber 14.
During sputter, the formation condition of film is as follows.Use Al-Ti(0.5%) make target, in Ar atmosphere, carry out sputter, making DC power is 7KW.
Second deposition step in the present embodiment is with 10000
Sedimentation velocity depositing Al-Ti film of/min, this film are the good films of a kind of transfer resistance, and its resistivity is 3.0-3.3 μ Ω .cm.
Use metallic membrane shown in Figure 4 to form device continuously,,, on above-mentioned substrate, form film under 200-650 ℃ of temperature condition of resistive heating in mode identical among the embodiment 17.
As a result, be under 160-450 ℃ the condition in the resistive heating temperature, obtain high-quality, the film of carbon containing, about 3 μ Ω .cm small resistor rates and high-reflectivity not.Preferable is that in the time of 260-440 ℃, it is higher that sedimentation velocity becomes, and is 100-800
/ min, and the circuit life-span is also long.The most preferably, temperature is 270-350 ℃, and in this scope, hillock density is extremely little, and the occurrence probability of the local turmoil of alloy lattice is also little.
Embodiment 17-22 is described above, with the exception of this, depositing Al in the first heavy step, and in second step depositing Al-Si-Ti, also be feasible.
In the foregoing description 17-22, because after selecting deposition of aluminum on the substrate, successive sedimentation is to be undertaken by the non-selective depositing metallic films that does not make substrate be exposed to outside air, so can form with high sedimentation velocity and have the good membranes characteristic, the metallic membrane of for example layering covering, electromigration etc.
Below, indicated is, each embodiment (23-28) that carries out with Fig. 4 (resistive heating) and Fig. 7 (direct heating) shown device.Embodiment 23-27 uses the device with better direct heating system (Fig. 7) to carry out, and the embodiment 28 then device of use with resistive heating system (Fig. 4) carries out.
At first prepare substrate.Substrate is a kind ofly on N type single-chip one deck SiO to be arranged
2Sample, described SiO
2Form through thermooxidizing, its thickness is 8000
At SiO
2The square sectional hole patterns to 100 μ m * square different size of 100 μ m of last printing 0.25 μ m * 0.25 μ m, the Si monocrystalline under making is exposed, makes sample with this.Fig. 2 A illustrates the part of substrate with synoptic diagram.Among the figure, the 1st, as the monocrystalline silicon substrate of semiconductor substrate, the 2nd, as the thermal oxidation silicon film of insulating film (layer).Be referred to as sample 1-1.VH
1And VH
2It is mutually different hole, aperture (exposed part).
The method that forms the Al-Si film on substrate 1 is as described below.
At first, substrate is placed in the material containing air lock 11.As mentioned above, hydrogen is introduced material containing air lock 11, the chamber of making is under the nitrogen atmosphere.With evacuation system 10 reaction chamber 12 inner pumpings are arrived about 1 * 10
-8Holder.
But, even the vacuum degree deficiency 1 * 10 in the reaction chamber 12
-8Holder also can form the Al-Si film.
DMAH and Si
2H
6Infeed by unshowned airway.As the vector gas by the DMAH conduit, that adopted is H
2
Unshowned second airway is used for carrying the H as reactant gases
2, by control the unshowned opening degree of letting out valve slowly with the pressure-controlling in the reaction chamber 12 in preset value.In this case, generally this pressure is transferred about 1.5 holders.Through the DMAH transfer lime DMAH is introduced in this reaction tubes.Stagnation pressure is about 1.5 holders, and the dividing potential drop of DMAH is about 1.5 * 10
-4Holder, and Si
2H
6Dividing potential drop be 2 * 10
-6Holder.Turn on light then with this sheet of direct heating.So just deposit Al-Si.Si
2H
6, SiH
4, Si
3H
8, Si(CH
3)
4, SiCl
4, SiH
2Cl
2, SiH
3Cl can be used as the silicon-containing gas in second unstripped gas in the process that forms the Al-Si film.
Add DMAH, H
2And such as Si
2H
6And so on contain Si unstripped gas, can deposit the Al-Si that contains 0.5-2.0%Si.The pressure of this reaction tubes is the 0.05-760 holder, and preferably 0.1-0.8 holder, substrate temperature is 260-440 ℃, the dividing potential drop of DMAH is 1 * 10 of a reaction tubes internal pressure
-5-1.3 * 10
-3Doubly, Si in the reaction tubes
2H
6Dividing potential drop then be its 1 * 10
-7-1 * 10
-4Doubly, deposit Al-Si whereby.
One predetermined excessively depositing time, the supply of DMAH just stops immediately.In this step, the predetermined depositing time of depositing Al-Si film is to make Si(monocrystalline silicon substrate 1) on the thickness of Al-Si film reach and SiO
2Required time when the film thickness of (through the silicon fiml 2 of thermooxidizing) equates.
At that time, substrate surface transfers to 270 ℃ through the temperature that direct heating reached.Above-mentioned steps is called first deposition step.By step so far, Al-Si film 3 just is deposited in the hole as shown in Figure 2.
After above-mentioned Al-Si deposition is finished, with evacuator device 10 CVD reaction chamber 12 is found time, reach 5 * 10 up to its vacuum tightness
-3Till holder or the littler value.Simultaneously, Rf etching chamber 13 is extracted into 5 * 10
-6Holder or littler value.After having determined that this two Room has all reached above-mentioned vacuum tightness, open gate valve 10, with transport unit (arm) 27 this substrate is moved to Rf etching chamber 13 from CVD reaction chamber 12, closing gate valve 10 then.
When this substrate was sent to Rf etching chamber 13, evacuator device was found time Rf etching chamber 13, reached 10 until its vacuum tightness
-6Till holder or the littler value.
Infeed the argon that etching is used by confession argon conduit 22 then, and in Rf etching chamber 13, keep 10
-1-10
-3The argon atmospher of holder.The base sheet rack of Rf etching maintains 200 ℃.The Rf of 100W is passed on the Rf etching electrode 21, lasts 30 seconds, argon is discharged so that with this substrate surface of argon ion etching in the Rf etching chamber, and remove the upper layer of CVD deposited film with this.In the case, etching depth is consistent with oxide skin, is about 100
In this explanation, in this Rf etching chamber, carry out surface etch to the CVD deposited film, but because defeated things such as on-chip cvd film upper layer oxygen-free through vacuum, so the Rf etching does not take place.Under the sort of situation, when the temperature difference of 14 of CVD reaction chamber 12 and sputtering chambers was big, Rf etching chamber 13 played a part to change the temperature-changing chamber that temperature is used at short notice.
After the Rf etching is finished in Rf etching chamber 13, stop argon and flow into, and the argon in the Rf etching chamber 13 is found time.Be pumped to 5 * 10 at Rf etching chamber 13
-6Holder, sputtering chamber is pumped to 14-5 * 10
-6After holder or the littler value, open gate valve 10.Then, with arm 27 substrate is moved to sputtering chamber 14 from Rf etching chamber 13.Closing gate valve 10 thereupon.
When substrate is transported to sputtering chamber 14 the insides, in Rf etching chamber 13 10
-1-10
-3In the argon atmospher of holder support 23 is transferred to 250 ℃.
In the present embodiment, make argon discharge and skim over target Al-Si(0.5% with argon ion with the 7KW dc power), with this on this substrate with 10000
/ minute sedimentation velocity depositing Al-Si.This step is non-selective deposition step.
This step is called the 2nd Al film deposition step.
On substrate, deposit 5000
The Al-Si film after, stop argon and flow into, and inactive direct supply.At load lock 11(15) be pumped to 5 * 10
-3 Gate valve 10 is opened in holder or more behind the low value, and mobile substrate.Behind the closing gate valve 10, N
2Gas flows into load lock 11(15), till reaching barometric point, substrate shifts out this device by gate valve 10 simultaneously.
In above-mentioned the 2nd Al film deposition step, the formation condition of film is as described below.Use Al-Si to make target, 10
-1-10
-3Under the pressure of holder, just formed film by the direct current energy of in Ar atmosphere, supplying with 5-10KW.At this moment, be heated by resistive substrate temperature is transferred to 200 ℃.
By the above-mentioned second metal film deposition step, as shown in Fig. 2 C, can 10000
/ minute speed at SiO
2Form the Al-Si film on the film.Deposit one deck Al as stated above.
And then, by reusing in kind this substrate of preparation, but by direct heating the surface temperature of this substrate is transferred to 280-480 ℃ specifically, the Al-Si film has just formed by first deposition step.Here, other filming condition in first deposition step and second deposition step is identical.
Equally, in first deposition step, also form the Al-Si film by the substrate surface temperature being transferred to 200-260 ℃ and 490-550 ℃.The result of gained identical with shown in the previous table 1.
By table 1 as seen, under the substrate surface temperature that changes in 260 ℃ of-400 ℃ of scopes that is reached by direct heating, Al is with 3000-5000
/ minute sedimentation velocity optionally be deposited in the hole.
By to being the Characteristics Detection of the Al film of surface temperature deposit in the hole of 260-440 ℃ substrate in scope, find that they are good: carbon containing not; Resistivity is 2.8-3.4 μ Ω .cm; Reflectivity is 90-95%; The density of 1 μ m or higher hillock is 0-10; The local turmoil of essentially no lattice (spike) produces (the bonded fracture probability of 0.15 μ m (breaking probability of 0.15 μ m bonding))
Certainly, also find with through sputter and contacting of Al-Si formed thereon is good, this is owing to the Al-Si film under it has the surface of good characteristic.
Otherwise under 200-250 ℃ substrate surface temperature, sedimentation velocity is then low to 1000-1500
/ minute, thereby output also be low to moderate the 7-10 sheet/hour.
On the other hand, when the substrate surface temperature surpassed 440 ℃, reflectivity just became 60% or littler, and the density of 1 μ m or higher hillock then is 10-10
4/ cm
2, local lattice turmoil production rate (spike generation) 0-30%, so the characteristic of the Al-Si film in this hole degenerates.
Then, on substrate sample, form Al-Si film as stated above with following structure.
On silicon single crystal as the first substrate surface material, form the silicon oxide film of one deck with the CVD method as the second substrate surface material, then, make monocrystalline silicon surface partly expose out by each lithography step printing figures.
The SiO of thermooxidizing
2Film thickness is 7000
, the silicon single crystal exposed part, promptly the hole is of a size of 0.25 μ m * 0.25 μ m to 10 μ m * 10 μ m.So just make this sample of sample 1-2(hereinafter referred to as " CVD SiO
2(be designated hereinafter simply as SiO
2/ silicon single crystal ").
Sample 1-3 is oxide film (being designated hereinafter simply as the BSG)/silicon single crystal with the doped with boron of atmospheric pressure cvd method formation,
Sample 1-4 is oxide film (being designated hereinafter simply as the PSG)/silicon single crystal with the Doping Phosphorus of atmospheric pressure cvd method formation,
Sample 1-5 is with the Doping Phosphorus of atmospheric pressure cvd method formation and oxide film (being designated hereinafter simply as the BSPG)/silicon single crystal of boron,
Sample 1-6 is nitride film (being designated hereinafter simply as the P-SiN)/silicon single crystal that forms with plasma CVD method,
Sample 1-7 is hot nitrided film (being designated hereinafter simply as T-SiN)/silicon single crystal,
Sample 1-8 is the nitrided film (being designated hereinafter simply as LP-SiN/ silicon single crystal) that forms with low voltage DC VD method, and
Sample 1-9 is nitrided film (being designated hereinafter simply as the ECR-SiN)/silicon single crystal that forms with the ECR device.In addition, all combinations according to the first substrate surface material and the second substrate surface material as follows have made sample 1-11 to 1-179.Adopt silicon single crystal (single crystalline Si), polysilicon (polycrystalline Si), amorphous silicon (non-crystalline state Si), tungsten (W), molybdenum (Mo), tantalum (Ta), tungsten silicide (WSi), titanium silicide (TiSi), aluminium (Al), aluminium silicon (Al-Si), titanium aluminium (Al-Ti), titanium nitride (TiN), copper (Cu), aluminium copper silicon (Al-Si-Cu), aluminium palladium (Al-Pd), titanium (Ti), copper silicide (Mo-Si), tantalum silicide (TaSi) as the first substrate surface material; Adopt T-SiO
2, SiO
2, BSG, PSG, BPSG, P-SiN, T-SiN, LP-SiN, ECR-SiN be as the second substrate surface material.To above-mentioned all samples and Yan Junke forms good Al film.
The embodiment of the invention 24 is used device shown in Figure 7, with DMAH and Si
2H
6Being unstripped gas, is reactant gases and method formation aluminium silicon (Al-Si) film of using halogen lamp direct heating substrate surface with hydrogen.
Be similar to embodiment 23, be prepared into and be covered with SiO on it with the square hole to the square various size of 100 μ m of many 0.25 μ m
2Monocrystalline silicon piece as substrate.On this substrate, CVD method is as described below carried out an Al-Si film deposition step, carries out the 2nd Al-Si film deposition step to form a kind of metallic membrane by sputtering method.
By with embodiment in same steps as, with DMAH, Si
2H
6Be passed to CVD reaction chamber 12 with hydrogen, to carry out the Al-Si deposition.
The condition that the one Al-Si film forms step is: total pressure 1.5 holders, DMAH dividing potential drop 1.5 * 10
-4Holder, the substrate surface temperature is 270 ℃.
By an above-mentioned Al-Si deposition step, with 3000-5000
/ minute sedimentation velocity, depositing Al-Si in the hole in different apertures obtains good selectivity whereby.Next step places sputtering chamber 14 with this substrate, is comprising SiO then
2On the whole surface of the Al-Si that becomes with this selective deposition, thickness is 5000 on the deposition
Al-Si.This sedimentation velocity is 10000
/ minute.
In addition, with same method, use with embodiment 23 in identical sample 1-11 to 1-179 as substrate to form the Al-Si film.In these all samples, all can form the good metal film by first and second deposition steps.
In above-mentioned each experiment, the substrate surface temperature all transfers to 270 ℃, and metal A l genus then forms by changing this condition from 200 ℃-550 ℃ every 10 ℃.
Discovery is similar to person shown in the table 1 by the characteristic of the Al-Si film of an Al-Si deposition step gained of all each samples.
Embodiment 25
Embodiment 25 has showed after an Al-Si deposition step that has carried out with embodiment 23, forms the Al-Si film with sputtering method as second deposition step on whole surface.Preparing a kind of structure and embodiment 23(sample 1-1) the identical substrate of substrate for use is as substrate.
By an above-mentioned Al-Si deposition step optionally behind the long-pending Al-Si of inner hole deposition, this substrate is placed sputtering chamber 14.Film formed condition is as follows in the sputter procedure:
Use Al-Cu(0.5%) be target, 5 * 10
-3Dc power in the argon atmospher of holder is 7KW.
By second deposition step among this embodiment, the Al-Cu film is with 10000
/ minute sedimentation velocity be deposited out because its resistivity is 3.0-3.3 μ Ω .cm, so this film splendid film that is transfer resistance.
By an above-mentioned Al-Si deposition step selectively after the long-pending Al-Si of inner hole deposition, this substrate is placed sputtering chamber 14.Film formation condition in the sputter procedure is as follows: use Al-Si(0.5%)-Cu(0.5%) being target, the dc power in the argon atmospher is 7KW.
Press second deposition step in the present embodiment, with 10000
/ minute sedimentation velocity deposit the Al-Si-Cu film because its resistivity is 3.0-3.3 μ Ω .cm, so this film is the splendid film of migration sheet resistance.
By an above-mentioned Al-Si deposition step optionally after inner hole deposition has amassed Al, this substrate is placed sputtering chamber 14.
Film formed condition is as follows in the sputter procedure: use Al-Ti(0.5%) make target, in Ar institute atmosphere, carry out sputter, dc power is 7KW.
Press second deposition step in the present embodiment with 10000
/ minute sedimentation velocity deposit the Al-Ti film because its resistivity is 3.0-3.3 μ Ω .cm, so this film splendid film that is transfer resistance.
Embodiment 28
Use the metallic membrane shown in Fig. 4 to form device continuously, under 200-650 ℃ temperature condition,, on above-mentioned substrate, form film with the method among the embodiment 23 by resistive heating.
As a result, obtain carbon-freely under 160-450 ℃ the temperature condition by resistive heating, its resistivity is little, is about 3 μ Ω .cm, the high-quality film that reflectivity is high.Better be in the time of 260-440 ℃, it is high to 100-800 that sedimentation velocity becomes
/ minute, and the circuit life-span is also high.Preferably temperature is 270-350 ℃, and in this scope hillock density minimum, the generation probability of the local turmoil of alloy lattice (alloy spike) is also low.
Embodiment 23-28 is described above, in addition also can be in first deposition step depositing Al-Si, and in second deposition step depositing Al-Si-Ti.
In the foregoing description 23-28, owing on substrate, be exposed to outside air depositing metallic films non-selectively with that after deposition of aluminum-silicon and don't with this substrate selectively, have splendid membrane property so can high sedimentation velocity form, cover the metallic membrane of (step coverage), electromigration etc. as level.
Embodiment 29
Use shown in Figure 9ly, the CVD assembling device that airing system is housed carries out the experiment described in the embodiment 1.
Purification pot is 1.4m to the duct length of CVD reaction chamber.The air leakage amount of finding the two is 5 * 10
-10Atm.cc/ second.The purity of hydrogen is the 99.99995-99.99999%(volume).When observing it and go up the existing film formed sample of Al, the result is basically with shown in the table 1 of front, but finds then that by experiment as described below the interplanar distribution of thicknesses of layers has become even.
Using itself is 5 inches Si sheet, to prepare each sample with the method among the embodiment 1.
Press Al-CVD method depositing Al in the hole selectively, measure the maximum value (m of Al film thickness
Max) and minimum value (m
Min), and remove (m with mean thickness m
Max-m
Min) value:
The result is that film thickness distribution S is 2-4%.
In view of being contained in CVD device outside when the hydrogen purification device, leave CVD reaction chamber 10m or longer distance, and when not using said apparatus, S then is the such fact of 5-10%, so can think present embodiment concerning the semiconducter device that a plurality of unit is made a slice, better effects if.
Claims (20)
1, form the method for metallic membrane, it comprises the steps:
In the space, settle for forming the substrate that film is used;
In described space, introduce alkyl aluminum hydride gas and hydrogen; And
The described substrate of direct heating is to form the metallic membrane of the aluminium that contains promising major ingredient on described substrate surface.
2, the described method of claim 1 is wherein carried out described direct heating with lamp.
3, the described method of claim 1, the surface temperature of wherein said substrate remains on 260-440 ℃ with described direct heating.
4, the described method of claim 1, wherein said metallic membrane is the aluminium monocrystalline.
5, the described method of claim 1, wherein said alkyl aluminum hydride is the dimethyl alanate.
6, form the method for metallic membrane, it comprises the steps:
In the space, settle for forming the used substrate of film;
In described space, introduce alkyl aluminum hydride gas, the gas that contains modifying element and hydrogen; And
The described substrate of direct heating, containing with formation on described substrate surface is the aluminium of main composition and the metallic membrane that contains described modifying element.
7, the described method of claim 6 is wherein carried out described direct heating with lamp.
8, the described method of claim 6, the surface temperature of wherein said substrate remains on 260-440 ℃ with described direct heating.
9, the described method of claim 6, wherein said alkyl aluminum hydride is the dimethyl alanate.
10, the described method of claim 6, wherein said modifying element are at least a element that is selected from Si, Ti and Cu.
11, form the method for metallic membrane, it may further comprise the steps:
In first film formation chamber, settle owing to semi-conductor and/or conductor part ground exposing the substrate that exposed part is arranged from being formed at this lip-deep insulation layer;
Introduce alkyl aluminum hydride gas and hydrogen to described first film formation chamber;
Keep described heating of substrate and selectively on described exposed part deposition contain metallic membrane for the aluminium of principal constituent; And
Under the condition of shielding outside air, described substrate is moved into second film formation chamber that is arranged near described first film formation chamber, and be placed in wherein, thereby shield outside air serially, and on described substrate, press vapor phase process formation metallic membrane.
12, the described method of claim 11, wherein said heating is the direct heating that carries out with lamp.
13, the described method of claim 11, the surface temperature of wherein said substrate remains on 260-440 ℃ through heating described substrate.
14, the described method of claim 11, wherein said alkyl aluminum hydride is the dimethyl alanate.
15, the described method of claim 11, the wherein said major ingredient that contains is that the metallic membrane of aluminium is the aluminium monocrystalline.
16, form the method for metallic membrane, it may further comprise the steps:
In first film formation chamber, settle owing to semi-conductor and/or conductor part ground exposing the substrate that exposed part is arranged from being formed at this lip-deep insulation layer;
Introduce alkyl aluminum hydride gas to described first film formation chamber, contain the gas and the hydrogen of modifying element;
Keep described heating of substrate, on described exposed part deposition, contain the metallic membrane that major ingredient is an aluminium selectively; And
Under the condition of shielding outside air, described substrate moved into be arranged near second film formation chamber of described first film formation chamber and be placed in wherein, thereby shield outside air serially, and on described substrate, press vapor phase process formation metallic membrane.
17, the described method of claim 16, wherein said heating is the direct heating that carries out with lamp.
18, the described method of claim 16, the surface temperature of wherein said substrate remains on 260-440 ℃ by heating this substrate surface.
19, the described method of claim 16, wherein said alkyl aluminum hydride is the dimethyl alanate.
20, the described method of claim 16, wherein said modifying element are at least a element that is selected from Si, Ti and Cu.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP036196/90 | 1990-02-19 | ||
| JP3619590 | 1990-02-19 | ||
| JP3619790 | 1990-02-19 | ||
| JP036197/90 | 1990-02-19 | ||
| JP3619490 | 1990-02-19 | ||
| JP3619690 | 1990-02-19 | ||
| JP036195/90 | 1990-02-19 | ||
| JP036194/90 | 1990-02-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1061445A true CN1061445A (en) | 1992-05-27 |
| CN1036860C CN1036860C (en) | 1997-12-31 |
Family
ID=27460225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91101919A Expired - Fee Related CN1036860C (en) | 1990-02-19 | 1991-02-19 | Process for forming metal deposited film containing aluminium as main component by use of alkly aluminium hydride |
Country Status (7)
| Country | Link |
|---|---|
| US (3) | US5151305A (en) |
| EP (1) | EP0448223B1 (en) |
| KR (1) | KR940006669B1 (en) |
| CN (1) | CN1036860C (en) |
| AT (1) | ATE139866T1 (en) |
| DE (1) | DE69120446T2 (en) |
| MY (1) | MY104628A (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029384B (en) * | 2005-11-16 | 2011-03-02 | Up化工株式会社 | A method for thin film vapor deposition of dialkyl amido dihydro aluminium compound |
| CN103021823A (en) * | 2012-12-15 | 2013-04-03 | 山东孚日光伏科技有限公司 | Non-vacuum stepping pass-type rapid selenizing device and selenizing method implemented by same |
| CN103021823B (en) * | 2012-12-15 | 2016-03-16 | 山东孚日光伏科技有限公司 | A kind of antivacuum stepping passing rapid selenium gasifying device and the selenizing method utilizing it to realize |
Also Published As
| Publication number | Publication date |
|---|---|
| MY104628A (en) | 1994-04-30 |
| EP0448223A2 (en) | 1991-09-25 |
| EP0448223B1 (en) | 1996-06-26 |
| DE69120446T2 (en) | 1996-11-14 |
| US5151305A (en) | 1992-09-29 |
| EP0448223A3 (en) | 1992-02-19 |
| ATE139866T1 (en) | 1996-07-15 |
| US6258174B1 (en) | 2001-07-10 |
| KR940006669B1 (en) | 1994-07-25 |
| DE69120446D1 (en) | 1996-08-01 |
| US5330633A (en) | 1994-07-19 |
| KR920000113A (en) | 1992-01-10 |
| JPH04214868A (en) | 1992-08-05 |
| CN1036860C (en) | 1997-12-31 |
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